JPWO2008126521A1 - Acrylic hollow particles, method for producing acrylic hollow particles, and cosmetics containing these particles - Google Patents
Acrylic hollow particles, method for producing acrylic hollow particles, and cosmetics containing these particles Download PDFInfo
- Publication number
- JPWO2008126521A1 JPWO2008126521A1 JP2009508975A JP2009508975A JPWO2008126521A1 JP WO2008126521 A1 JPWO2008126521 A1 JP WO2008126521A1 JP 2009508975 A JP2009508975 A JP 2009508975A JP 2009508975 A JP2009508975 A JP 2009508975A JP WO2008126521 A1 JPWO2008126521 A1 JP WO2008126521A1
- Authority
- JP
- Japan
- Prior art keywords
- acrylic
- meth
- weight
- particles
- hollow particles
- 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 252
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000002537 cosmetic Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 102
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 36
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000009477 glass transition Effects 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 35
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 239000003505 polymerization initiator Substances 0.000 claims description 20
- 229920001519 homopolymer Polymers 0.000 claims description 18
- 239000012736 aqueous medium Substances 0.000 claims description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 9
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims 2
- 239000004677 Nylon Substances 0.000 abstract description 27
- 229920001778 nylon Polymers 0.000 abstract description 27
- 206010016322 Feeling abnormal Diseases 0.000 abstract description 20
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 229940048053 acrylate Drugs 0.000 description 34
- 238000000034 method Methods 0.000 description 27
- -1 foundations Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000003995 emulsifying agent Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- 239000004342 Benzoyl peroxide Substances 0.000 description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229940114077 acrylic acid Drugs 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 210000004209 hair Anatomy 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 230000001953 sensory effect Effects 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000013268 sustained release Methods 0.000 description 3
- 239000012730 sustained-release form Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 241000894007 species Species 0.000 description 2
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- KFSQJVOLYQRELE-HWKANZROSA-N (e)-2-ethylbut-2-enoic acid Chemical compound CC\C(=C/C)C(O)=O KFSQJVOLYQRELE-HWKANZROSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- DRMLUOBCBKAWMM-UHFFFAOYSA-N 1-methoxy-1-oxotetradecane-2-sulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCC(S(O)(=O)=O)C(=O)OC DRMLUOBCBKAWMM-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- DGSZGZSCHSQXFV-UHFFFAOYSA-N 2,3-bis(2-ethylhexanoyloxy)propyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(OC(=O)C(CC)CCCC)COC(=O)C(CC)CCCC DGSZGZSCHSQXFV-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- SJNWVJGWEJCMEY-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;phthalic acid Chemical compound OCCOCCO.OC(=O)C1=CC=CC=C1C(O)=O SJNWVJGWEJCMEY-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-ARJAWSKDSA-M 2-Methyl-2-butenoic acid Natural products C\C=C(\C)C([O-])=O UIERETOOQGIECD-ARJAWSKDSA-M 0.000 description 1
- SPSNALDHELHFIJ-UHFFFAOYSA-N 2-[(1-cyano-1-cyclopropylethyl)diazenyl]-2-cyclopropylpropanenitrile Chemical compound C1CC1C(C)(C#N)N=NC(C)(C#N)C1CC1 SPSNALDHELHFIJ-UHFFFAOYSA-N 0.000 description 1
- OWTQQPNDSWCHOV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO OWTQQPNDSWCHOV-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical class OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- DDBYLRWHHCWVID-UHFFFAOYSA-N 2-ethylbut-1-enylbenzene Chemical compound CCC(CC)=CC1=CC=CC=C1 DDBYLRWHHCWVID-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- OZPOYKXYJOHGCW-UHFFFAOYSA-N 2-iodoethenylbenzene Chemical compound IC=CC1=CC=CC=C1 OZPOYKXYJOHGCW-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical class OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 1
- ZTHJQCDAHYOPIK-UHFFFAOYSA-N 3-methylbut-2-en-2-ylbenzene Chemical compound CC(C)=C(C)C1=CC=CC=C1 ZTHJQCDAHYOPIK-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- YAXPDWVRLUOOBJ-UHFFFAOYSA-N 4-ethylhex-3-en-3-ylbenzene Chemical compound CCC(CC)=C(CC)C1=CC=CC=C1 YAXPDWVRLUOOBJ-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001237961 Amanita rubescens Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BWHOZHOGCMHOBV-UHFFFAOYSA-N benzylideneacetone Chemical compound CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 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
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- RTVSUIOGXLXKNM-UHFFFAOYSA-N dec-1-enylbenzene Chemical compound CCCCCCCCC=CC1=CC=CC=C1 RTVSUIOGXLXKNM-UHFFFAOYSA-N 0.000 description 1
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- VGIYPVFBQRUBDD-UHFFFAOYSA-N ethenoxycyclohexane Chemical compound C=COC1CCCCC1 VGIYPVFBQRUBDD-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000037308 hair color Effects 0.000 description 1
- 239000003676 hair preparation Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- RCALDWJXTVCBAZ-UHFFFAOYSA-N oct-1-enylbenzene Chemical compound CCCCCCC=CC1=CC=CC=C1 RCALDWJXTVCBAZ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000004761 scalp Anatomy 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本発明は、ナイロン粒子より遥かに廉価に製造でき、かつ、ナイロン粒子と同等または近似するソフト感、しっとり感、伸展性を有するアクリル中空粒子、この粒子の製造方法、およびこの粒子を含有する化粧料を提供することを目的とするものであり、本発明のアクリル中空粒子は、ホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）と、不飽和二重結合を２個以上有するモノマー（Ａ−２）との共重合体、および（メタ）アクリル系ポリマー（Ｂ）からなるアクリル中空粒子であって、（Ａ−１）が４５〜９０重量％、（Ａ−２）が１０〜５５重量％の割合で共重合され、開口部が所定の寸法で形成されていることを特徴としており、さらに本発明はアクリル中空粒子の粒子の製造方法、およびこの粒子を含有する化粧料を提供する。The present invention relates to acrylic hollow particles that can be produced at a much lower price than nylon particles and have a soft feeling, moist feeling, and extensibility equivalent to or similar to nylon particles, a method for producing the particles, and a cosmetic containing the particles The acrylic hollow particles of the present invention are provided with a non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or lower and a non-crosslinkable monomer. Acrylic hollow particles comprising a copolymer with a monomer (A-2) having two or more saturated double bonds and a (meth) acrylic polymer (B), wherein (A-1) is 45 to 90 weights %, (A-2) is copolymerized at a ratio of 10 to 55% by weight, and the opening is formed with a predetermined size. The present invention further provides a method for producing particles of acrylic hollow particles , And to provide a cosmetic containing the particles.
Description
本発明は、アクリル中空粒子、アクリル中空粒子の製造方法、およびこの粒子を含有する化粧料に関する。さらに詳しくは、所定の大きさの孔を有し、ナイロン粒子に近い感触が得られるアクリル中空粒子、アクリル中空粒子の製造方法、およびこの粒子を含有する化粧料に関する。 The present invention relates to acrylic hollow particles, a method for producing acrylic hollow particles, and a cosmetic containing the particles. More specifically, the present invention relates to acrylic hollow particles having pores of a predetermined size and providing a feeling close to that of nylon particles, a method for producing acrylic hollow particles, and a cosmetic containing the particles.
ファンデーションなどの化粧料には、ソフト感、しっとり感、伸展性（肌の上での伸び）などの機能を付与させることを目的として、ナイロン粒子、アクリル粒子、ウレタン粒子、ポリエチレン粒子などの粒子を配合している。これらの粒子のうち、ソフト感、しっとり感、伸展性などの機能面に最も優れているのは、ナイロン粒子である。しかし、化粧料用のナイロン粒子は、環状ラクタムをアルカリ重合触媒の存在下で、特異な溶液沈殿法によって製造されるため（たとえば、特許文献１参照）、アクリル粒子などに比べ製造コストが極めて高い。そのため、ナイロン粒子を配合できる化粧料は、価格が高い高級品に限定されている。 For cosmetics such as foundations, particles such as nylon particles, acrylic particles, urethane particles, polyethylene particles, etc. are used for the purpose of imparting functions such as soft feeling, moist feeling, and extensibility (elongation on the skin). It is blended. Among these particles, nylon particles are most excellent in functional aspects such as soft feeling, moist feeling, and extensibility. However, since nylon particles for cosmetics are produced by a specific solution precipitation method using cyclic lactam in the presence of an alkali polymerization catalyst (see, for example, Patent Document 1), the production cost is extremely high compared to acrylic particles and the like. . Therefore, cosmetics that can be blended with nylon particles are limited to high-priced luxury products.
これに対し、アクリル粒子は、伸展性に優れ、ナイロン粒子より廉価であるため、一般の化粧料には使用されている。しかし、ソフト感、およびしっとり感はナイロン粒子に比べかなり劣る欠点があるが、近年、様々な改良品が提案されている。特許文献２には、所定の架橋（メタ）アクリル酸エステル系樹脂からなる多孔質樹脂微粒子で、所定の圧縮強度および復元率を有する微粒子を外用剤に配合すると、伸展性および感触性に優れていることが記載されている。しかし、本発明者が行った実験によると、特許文献２に記載された多孔質樹脂微粒子は、ナイロン粒子ほどのソフト感、しっとり感が得られないことが確認された。 On the other hand, acrylic particles have excellent extensibility and are less expensive than nylon particles, and are therefore used in general cosmetics. However, soft feeling and moist feeling are disadvantageous inferior to nylon particles, but various improved products have been proposed in recent years. In Patent Document 2, when porous resin fine particles made of a predetermined crosslinked (meth) acrylic acid ester-based resin and having a predetermined compressive strength and restoration rate are blended in an external preparation, excellent extensibility and feel are obtained. It is described that. However, according to an experiment conducted by the present inventor, it was confirmed that the porous resin fine particles described in Patent Document 2 do not have a soft feeling and a moist feeling as much as nylon particles.
また、引用文献３には、多官能性モノマーの重合体と単官能性モノマーの重合体との混合物からなる中空微粒子、およびその簡単な製造方法について記載されている。しかし、引用文献３に記載された中空微粒子は、媒体内での微粉末の分散補助などに用いられ、化粧料用の中空粒子として、ソフト感、しっとり感、伸展性に優れていることは何ら記載されていない。
上記実情に鑑み、本発明者は、上記諸欠点を解消したアクリル中空粒子を提供すべく、鋭意検討した結果完成するに至ったものである。すなわち、本発明の目的は、ナイロン粒子より遥かに廉価に製造でき、かつ、ナイロン粒子と同等または近似するソフト感、しっとり感、伸展性を有するアクリル中空粒子、この粒子の製造方法、およびこの粒子を含有する化粧料を提供することにある。 In view of the above circumstances, the present inventor has completed as a result of earnest studies to provide acrylic hollow particles that have solved the above-mentioned drawbacks. That is, it is an object of the present invention to produce acrylic hollow particles having a soft feeling, moist feeling, and extensibility equivalent to or similar to nylon particles, and a method for producing the particles, and the particles. It is providing the cosmetics containing this.
第１発明は、ホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）と、不飽和二重結合を２個以上有するモノマー（Ａ−２）との共重合体、および（メタ）アクリル系ポリマー（Ｂ）からなるアクリル中空粒子であって、
前記ホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）が４５〜９０重量％、前記不飽和二重結合を２個以上有するモノマー（Ａ−２）が１０〜５５重量％の割合で共重合され、
前記アクリル中空粒子は、中空であるコアと外殻であるシェルとを備え、
前記アクリル中空粒子のシェルの外径（α）は３〜１０μｍであり、
シェルの外径（α）とコアの径（β）との比｛（α）／（β）｝が、１．１〜３．５であり、
前記シェルには、前記コアに通じる孔が２以上形成され、
前記２以上の孔のうち最大の孔の径（γ）が、０．３〜２．５μｍであり、
前記コアの径（β）と前記最大の孔の径（γ）との比｛（β）／（γ）｝が、１．１〜２５．０であることを特徴とするアクリル中空粒子である。The first invention relates to a non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or lower and a monomer (A-2) having two or more unsaturated double bonds A hollow acrylic particle comprising a copolymer of (meth) acrylic polymer (B),
Non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or lower of the homopolymer is 45 to 90% by weight, and a monomer having two or more unsaturated double bonds (A-2) ) Is copolymerized in a proportion of 10 to 55% by weight,
The acrylic hollow particle comprises a hollow core and a shell that is an outer shell,
The outer diameter (α) of the shell of the acrylic hollow particles is 3 to 10 μm,
The ratio {(α) / (β)} of the shell outer diameter (α) to the core diameter (β) is 1.1 to 3.5,
In the shell, two or more holes leading to the core are formed,
Of the two or more holes, the largest hole diameter (γ) is 0.3 to 2.5 μm,
Acrylic hollow particles characterized in that the ratio {(β) / (γ)} of the core diameter (β) to the maximum pore diameter (γ) is 1.1 to 25.0. .
また、第２発明は、ホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）、不飽和二重結合を２個以上有するモノマー（Ａ−２）、重合開始剤（Ｃ）、および水性媒体（Ｄ）を混合、撹拌して水性分散液を調製し、
ついで、得られた水性分散液に、別途に調製した（メタ）アクリル系ポリマー（Ｂ）を水性媒体に分散させたシード粒子分散液を混合、撹拌し、前記水性分散液に含有するホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）、および不飽和二重結合を２個以上有するモノマー（Ａ−２）を前記（メタ）アクリル系ポリマー（Ｂ）に吸収させ、
ついで、得られた（メタ）アクリル系ポリマーを含有する水性分散液を加熱して、前記ホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）と、前記不飽和二重結合を２個以上有するモノマー（Ａ−２）とを共重合させて得る、アクリル中空粒子の製造方法であって、
前記ホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）が４５〜９０重量％、前記不飽和二重結合を２個以上有するモノマー（Ａ−２）が１０〜５５重量％の割合で共重合され、
得られるアクリル中空粒子は、中空であるコアと外殻であるシェルとを備え、
得られるアクリル中空粒子のシェルの外径（α）は、３〜１０μｍであり、
シェルの外径（α）とコアの径（β）との比｛（α）／（β）｝が、１．１〜３．５であり、
前記シェルには、前記コアに通じる孔が２以上形成され、
前記２以上の孔のうち最大の孔の径（γ）が、０．３〜２．５μｍであり、
前記コアの径（β）と前記最大の孔の径（γ）との比｛（β）／（γ）｝が、１．１〜２５．０であることを特徴とする、アクリル中空粒子の製造方法である。Further, the second invention relates to a non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or lower and a monomer (A-2) having two or more unsaturated double bonds. , Polymerization initiator (C), and aqueous medium (D) are mixed and stirred to prepare an aqueous dispersion,
Next, a seed particle dispersion in which the separately prepared (meth) acrylic polymer (B) is dispersed in an aqueous medium is mixed and stirred into the obtained aqueous dispersion, and the homopolymer contained in the aqueous dispersion is stirred. A non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or lower, and a monomer (A-2) having two or more unsaturated double bonds are added to the (meth) acrylic polymer ( B)
Subsequently, the obtained aqueous dispersion containing the (meth) acrylic polymer is heated to form a non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or less. A method for producing acrylic hollow particles obtained by copolymerizing the monomer (A-2) having two or more unsaturated double bonds,
Non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or lower of the homopolymer is 45 to 90% by weight, and a monomer having two or more unsaturated double bonds (A-2) ) Is copolymerized in a proportion of 10 to 55% by weight,
The resulting acrylic hollow particles comprise a hollow core and a shell that is an outer shell,
The outer diameter (α) of the shell of the resulting acrylic hollow particles is 3 to 10 μm,
The ratio {(α) / (β)} of the shell outer diameter (α) to the core diameter (β) is 1.1 to 3.5,
In the shell, two or more holes leading to the core are formed,
Of the two or more holes, the largest hole diameter (γ) is 0.3 to 2.5 μm,
A ratio of the core diameter (β) to the maximum pore diameter (γ) {(β) / (γ)} is 1.1 to 25.0. It is a manufacturing method.
本発明は、次のような特別に優れた効果を奏し、その産業上の利用価値は極めて大である。 The present invention has the following particularly excellent effects, and its industrial utility value is extremely great.
１．本発明に係るアクリル中空粒子は、製造コストがナイロン粒子より遥かに廉価であるので、高級化粧料のみならず、多種多様な化粧料に配合することができる。 1. Since the acrylic hollow particles according to the present invention are much cheaper to manufacture than nylon particles, they can be blended not only in high-grade cosmetics but also in a wide variety of cosmetics.
２．本発明に係るアクリル中空粒子は、ホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマーと、不飽和二重結合を２個以上有するモノマーとを特定の割合で共重合したものを主成分とし、かつ、所定の大きさの孔を有するので、ナイロン粒子と同等のソフト感、しっとり感を有し、心地よい触感を与える。 2. The hollow acrylic particles according to the present invention include a non-crosslinkable (meth) acrylic acid ester monomer having a homopolymer glass transition temperature of 50 ° C. or less and a monomer having two or more unsaturated double bonds at a specific ratio. Since it has a polymerized main component and has pores of a predetermined size, it has a soft feeling and a moist feeling equivalent to those of nylon particles, and gives a pleasant touch feeling.
３．本発明に係るアクリル粒子の製造方法は、疎水性有機溶剤を使用しないので、得られるアクリル中空粒子は、時間が経過しても粒子の膨潤・融着を引き起こし難く、長期安定性に優れている。 3. Since the method for producing acrylic particles according to the present invention does not use a hydrophobic organic solvent, the resulting acrylic hollow particles are less likely to cause swelling and fusion of the particles over time and have excellent long-term stability. .
４．本発明に係るアクリル中空粒子を含有する化粧料は、ソフト感、しっとり感、および伸展性に優れているので、使い心地が良い。 4). Since the cosmetic containing the acrylic hollow particles according to the present invention is excellent in soft feeling, moist feeling, and extensibility, it is comfortable to use.
本発明に係るアクリル中空粒子は、ホモポリマーのガラス転移温度（以下、Ｔｇと略記する）が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）と不飽和二重結合を２個以上有するモノマー（Ａ−２）との共重合体、および（メタ）アクリル系ポリマー（Ｂ）を主成分として調製される。なお、本発明において（メタ）アクリル酸とは、アクリル酸とメタクリル酸の双方を意味し、（メタ）アクリレートとは、アクリレートとメタクリレートの双方を意味する。
＜アクリル中空粒子の調製に用いられる原料＞
ホモポリマーのＴｇが５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）
本発明に用いられる（Ａ−１）成分は、ホモポリマーのＴｇが５０℃以下であることを
必須とする。ホモポリマーのＴｇが５０℃を超えると、得られるアクリル中空粒子が、ソフト感およびしっとり感に劣るので好ましくない。The acrylic hollow particles according to the present invention comprise a non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature (hereinafter abbreviated as Tg) of a homopolymer of 50 ° C. or less and an unsaturated double bond. It is prepared mainly with a copolymer with two or more monomers (A-2) and a (meth) acrylic polymer (B). In the present invention, (meth) acrylic acid means both acrylic acid and methacrylic acid, and (meth) acrylate means both acrylate and methacrylate.
<Raw materials used for the preparation of acrylic hollow particles>
Non-crosslinkable (meth) acrylic acid ester monomer (A-1) having homopolymer Tg of 50 ° C. or lower
The component (A-1) used in the present invention requires that the Tg of the homopolymer is 50 ° C. or lower. If the Tg of the homopolymer exceeds 50 ° C., the resulting acrylic hollow particles are not preferable because they are inferior in soft feeling and moist feeling.
Ｔｇが５０℃以下の非架橋性（メタ）アクリル酸エステルモノマーの例としては、メチルアクリレート、エチルアクリレート、ブチルアクリレート、イソブチルアクリレート、ヘキシルアクリレート、２−エチルヘキシルアクリレート、２−ヒドロキシエチルアクリレートなどのアクリル酸エステル；ブチルメタクリレート、イソブチルメタクリレート、ヘキシルメタクリレート、２−エチルヘキシルメタクリレートなどのメタクリル酸エステルが挙げられる。これらの中では、ブチルアクリレートが好ましい。これらのＴｇが５０℃以下の非架橋性（メタ）アクリル酸エステルモノマーは、単独または２種以上を組み合わせて使用することができる。 Examples of non-crosslinkable (meth) acrylate monomers having a Tg of 50 ° C. or lower include acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate. Esters: Methacrylic acid esters such as butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate. Of these, butyl acrylate is preferred. These non-crosslinkable (meth) acrylic acid ester monomers having a Tg of 50 ° C. or less can be used alone or in combination of two or more.
また、得られるアクリル中空粒子の性能が低下しない範囲であれば、ホモポリマーのＴｇが５０℃以下の非架橋性（メタ）アクリル酸エステルモノマーと、共重合可能なモノマーとを併用することができる。共重合可能なモノマーの例としては、ホモポリマーのＴｇが５０℃を超える非架橋性（メタ）アクリル酸エステルモノマー、モノビニル芳香族モノマー、ビニルエステル系モノマー、ビニルエーテル系モノマー、モノオレフィン系モノマー、ハロゲン化オレフィン系モノマー、ジオレフィン、アクリル酸、メタクリル酸などが挙げられる。併用するモノマーは、単独または２種以上を組み合わせて使用することができる。 Moreover, as long as the performance of the resulting acrylic hollow particles does not deteriorate, a non-crosslinkable (meth) acrylic acid ester monomer having a homopolymer Tg of 50 ° C. or lower and a copolymerizable monomer can be used in combination. . Examples of copolymerizable monomers include non-crosslinkable (meth) acrylic acid ester monomers, monovinyl aromatic monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, halogens whose homopolymer Tg exceeds 50 ° C. Olefinic monomers, diolefins, acrylic acid, methacrylic acid and the like. The monomers used in combination can be used alone or in combination of two or more.
ホモポリマーのＴｇが５０℃を超える非架橋性（メタ）アクリル酸エステルモノマーの例としては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸−２−ヒドロキシエチルなどが挙げられる。モノビニル芳香族モノマーとしては、スチレン、α−メチルスチレン、ビニルトルエン、α−クロロスチレン、ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン、スチレンスルホン酸ナトリウムなどが挙げられる。ビニルエステル系モノマーとしては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニルなどが挙げられる。ビニルエーテル系モノマーとしては、ビニルメチルエーテル、ビニルエチルエーテル、ビニル-ｎ−ブチルエーテル、ビニルフェニルエーテル、ビニルシクロヘキシルエーテルなどが挙げられる。 Examples of non-crosslinkable (meth) acrylic acid ester monomers whose Tg of the homopolymer exceeds 50 ° C. include methyl methacrylate, ethyl methacrylate, and 2-hydroxyethyl methacrylate. Examples of the monovinyl aromatic monomer include styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, sodium styrenesulfonate, and the like. Examples of vinyl ester monomers include vinyl formate, vinyl acetate, and vinyl propionate. Examples of vinyl ether monomers include vinyl methyl ether, vinyl ethyl ether, vinyl-n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like.
モノオレフィン系モノマーの例としては、エチレン、プロピレン、ブテン−１、ペンテン−１、４−メチルペンテン−１などが挙げられる。ハロゲン化オレフィン系モノマーとしては、塩化ビニル、塩化ビニリデンなどが挙げられる。ジオレフィン類としては、ブタジエン、イソプレン、クロロプレンなどが挙げられる。 Examples of monoolefin monomers include ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1. Examples of the halogenated olefin monomer include vinyl chloride and vinylidene chloride. Diolefins include butadiene, isoprene, chloroprene and the like.
なお、ホモポリマーのＴｇが５０℃以下の非架橋性（メタ）アクリル酸エステルモノマーと、共重合可能なモノマーとを併用する場合には、得られる共重合体のＴgが５０℃以下にしなければならない。なお、共重合体のＴｇは、公知の方法で測定できるが、次に示すＦｏｘの式より算出してもよい。
１／Ｔｇ＝Σ（Ｗｎ／Ｔｇｎ）／１００
この式で、Ｗｎはモノマーｎの重量％、ＴｇｎはモノマーｎからなるホモポリマーのＴｇを示す。
不飽和二重結合を２個以上有するモノマー（Ａ−２）
本発明に用いられる（Ａ−２）成分としては、多官能（メタ）アクリル酸エステル系モノマー、芳香族ジビニル系モノマーなどの重合性Ｃ＝Ｃ２重結合を２個以上（特に、２〜４個）有するモノマーが好ましい。When a non-crosslinkable (meth) acrylic acid ester monomer having a homopolymer Tg of 50 ° C. or less and a copolymerizable monomer are used in combination, the resulting copolymer must have a Tg of 50 ° C. or less. Don't be. The Tg of the copolymer can be measured by a known method, but may be calculated from the following Fox equation.
1 / Tg = Σ (Wn / Tgn) / 100
In this formula, Wn represents the weight percent of monomer n, and Tgn represents the Tg of a homopolymer comprising monomer n.
Monomer having two or more unsaturated double bonds (A-2)
As the component (A-2) used in the present invention, two or more polymerizable C═C double bonds such as a polyfunctional (meth) acrylic acid ester monomer and an aromatic divinyl monomer are used (particularly 2 to 4). ) Is preferred.
多官能（メタ）アクリル酸エステル系モノマーの例としては、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、デカエチレングリコールジ（メタ）アクリレート、ペンタデカエチレングリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリストールテトラ（メタ）アクリレート、フタル酸ジエチレングリコールジ（メタ）アクリレート、カプロラクトン変性ジペンタエリスルトールヘキサ（メタ）アクリレート、カプロラクトン変性ヒドロキシピバリン酸エステルネオペンチルグリコールジアクリレート、ポリエステルアクリレート、ウレタンアクリレートなどが挙げられる。芳香族ジビニル系モノマーの例としては、ジビニルベンゼン、ジビニルビフェニル、ジビニルナフタレン、ジアリルフタレートおよびこれらの誘導体が挙げられる。上記の不飽和二重結合を２個以上有するモノマーは、単独または２種以上を組み合わせて使用することができる。 Examples of polyfunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, pentadeca Ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol phthalate di (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) a Relate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate, polyester acrylate, and urethane acrylate. Examples of the aromatic divinyl monomer include divinylbenzene, divinylbiphenyl, divinylnaphthalene, diallyl phthalate, and derivatives thereof. Monomers having two or more unsaturated double bonds may be used alone or in combination of two or more.
上記の（Ａ−１）成分および（Ａ−２）成分は、（Ａ−１）成分が４５〜９０重量％、（Ａ−２）成分が１０〜５５重量％の割合で共重合される。（Ａ−２）成分が１０重量％より少なくなると、目的とする所定の形状の粒子が得られず、また、（Ａ−２）成分が５５重量％より多くなると、得られる粒子の弾力性が低下し、ソフト感、しっとり感に劣るため、好ましくない。より好ましい共重合比は、（Ａ−１）成分が５０〜８０重量％、（Ａ−２）成分が２０〜５０重量％の割合である。
（メタ）アクリル系ポリマー（Ｂ）
本発明に用いられる（Ｂ）成分は、（メタ）アクリル酸アルキルエステル（共）重合体により構成される。The components (A-1) and (A-2) are copolymerized in such a proportion that the component (A-1) is 45 to 90% by weight and the component (A-2) is 10 to 55% by weight. When the amount of the component (A-2) is less than 10% by weight, the target particles having a predetermined shape cannot be obtained. When the amount of the component (A-2) is more than 55% by weight, the elasticity of the obtained particles is increased. It is not preferable because it is lowered and soft and moist. A more preferable copolymerization ratio is a ratio of 50 to 80% by weight of the component (A-1) and 20 to 50% by weight of the component (A-2).
(Meth) acrylic polymer (B)
(B) component used for this invention is comprised by the (meth) acrylic-acid alkylester (co) polymer.
（Ｂ）成分として使用できる（メタ）アクリル酸アルキルエステルの例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロへキシル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−プロピル（メタ）アクリレート、クロロ−２−ヒドロキシエチル（メタ）アクリレート、ジエチレングリコールモノ（メタ）アクリレート、メトキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレートおよびイソボロノル（メタ）アクリレートなどが挙げられる。これらの（メタ）アクリル酸アルキルエステルは、単独または２種以上を組み合わせて使用することができる。 Examples of (meth) acrylic acid alkyl ester that can be used as the component (B) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-propyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate , Diethylene glycol mono (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and isoboronor (meth) ) Such as acrylate, and the like. These (meth) acrylic acid alkyl esters can be used alone or in combination of two or more.
（Ｂ）成分は、（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマーとが共重合されていてもよく、共重合可能な他のモノマーとしては、スチレン系モノマー、ビニル系モノマー、不飽和カルボン酸モノマーなどが挙げられる。 Component (B) may be copolymerized with other monomers copolymerizable with (meth) acrylic acid alkyl ester. Examples of other copolymerizable monomers include styrene monomers, vinyl monomers, And saturated carboxylic acid monomers.
（メタ）アクリル酸アルキルエステルと共重合できるスチレン系モノマーの例としては、スチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、ジエチルスチレン、トリエチルスチレン、プロピルスチレン、ブチルスチレン、へキシルスチレン、ヘプチルスチレンおよびオクチルスチレンなどのアルキルスチレン；フロロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨウドスチレンおよびクロロメチルスチレンなどのハロゲン化スチレン；ならびに、ニトロスチレン、アセチルスチレンおよびメトキシスチレンなどが挙げられる。 Examples of styrenic monomers that can be copolymerized with (meth) acrylic acid alkyl esters include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl. Alkyl styrenes such as styrene and octyl styrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene and chloromethylstyrene; and nitrostyrene, acetylstyrene and methoxystyrene.
ビニル系モノマーの例としては、ビニルピリジン、ビニルピロリドン、ビニルカルバゾール、ビニルアセテートおよびアクリロニトリル；ブタジエン、イソプレンおよびクロロプレンなどの共役ジエンモノマー；塩化ビニルおよび臭化ビニルなどのハロゲン化ビニル；塩化ビニリデンなどのハロゲン化ビニリデンなどが挙げられる。また、不飽和カルボン酸モノマーとしては、（メタ）アクリル酸、α-エチル（メタ）アクリル酸、クロトン酸、α-メチルクロトン酸、α-エチルクロトン酸、イソクロトン酸、チグリン酸およびウンゲリカ酸などの付加重合性不飽和脂肪族モノカルボン酸；マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸、グルタコン酸およびヒドロムコン酸などの付加重合性不飽和脂肪族ジカルボン酸などが挙げられる。 Examples of vinyl-based monomers include vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, vinyl acetate and acrylonitrile; conjugated diene monomers such as butadiene, isoprene and chloroprene; vinyl halides such as vinyl chloride and vinyl bromide; halogens such as vinylidene chloride And vinylidene chloride. Further, as unsaturated carboxylic acid monomers, (meth) acrylic acid, α-ethyl (meth) acrylic acid, crotonic acid, α-methylcrotonic acid, α-ethylcrotonic acid, isocrotonic acid, tiglic acid, ungelic acid, etc. Addition-polymerizable unsaturated aliphatic monocarboxylic acid; addition-polymerizable unsaturated aliphatic dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid and hydromuconic acid.
さらに、（Ｂ）成分は、上記の（メタ）アクリル酸アルキルエステル、および必要に応じて（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマーのほかに、不飽和二重結合を２個以上有するモノマーとを共重合した架橋構造を形成したものでもよい。不飽和二重結合を２個以上有するモノマーとしては、前記（Ａ−２）成分で記載したモノマーを使用することができる。 Further, the component (B) contains two unsaturated double bonds in addition to the above (meth) acrylic acid alkyl ester and, if necessary, other monomers copolymerizable with the (meth) acrylic acid alkyl ester. What formed the crosslinked structure which copolymerized the monomer which has the above may be used. As the monomer having two or more unsaturated double bonds, the monomers described in the component (A-2) can be used.
（Ｂ）成分として、（メタ）アクリル酸アルキルエステルと、（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマーおよび／または不飽和二重結合を２個以上有するモノマーからなる共重合体を用いるときには、（メタ）アクリル酸アルキルエステルが１００重量部に対して、（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマーが０〜２０重量部、不飽和二重結合を２個以上有するモノマーが０．００５〜０．０５重量部の割合で共重合させるのが好ましい。 As the component (B), a copolymer comprising (meth) acrylic acid alkyl ester, another monomer copolymerizable with (meth) acrylic acid alkyl ester and / or a monomer having two or more unsaturated double bonds. When used, the amount of (meth) acrylic acid alkyl ester is 100 parts by weight, the other monomer copolymerizable with (meth) acrylic acid alkyl ester is 0 to 20 parts by weight, and has two or more unsaturated double bonds. The monomer is preferably copolymerized in a proportion of 0.005 to 0.05 parts by weight.
本発明において、（Ｂ）成分は、前記した（メタ）アクリル酸アルキルエステル、必要に応じて（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマーを、ソープフリー乳化重合、乳化重合、懸濁重合、シード重合などの水系の重合方法によりシード粒子に調製するのが好ましい。これらの重合方法の中でより好ましいのは、粒度分布が狭い粒子が得られる理由から、ソープフリー乳化重合による調製である。 In the present invention, the component (B) contains the above-mentioned (meth) acrylic acid alkyl ester and, if necessary, other monomers copolymerizable with the (meth) acrylic acid alkyl ester, soap-free emulsion polymerization, emulsion polymerization, It is preferable to prepare seed particles by an aqueous polymerization method such as turbid polymerization or seed polymerization. More preferable among these polymerization methods is preparation by soap-free emulsion polymerization because particles having a narrow particle size distribution can be obtained.
ソープフリー乳化重合によりシード粒子を含有する懸濁液を調製する場合には、通常、重合開始剤を使用する。使用される重合開始剤としては、重合の際に使用される水性媒体に可溶な重合開始剤であればよく、好ましいのは過硫酸カリウム、過硫酸アンモニウムである。重合開始剤の使用量は、ソープフリー乳化重合の際に使用される上記モノマー１００重量部に対して、０．１〜１０重量部の範囲が好ましい。また、水性媒体は、後記する水性媒体（Ｄ）をいずれも用いることができる。 When preparing a suspension containing seed particles by soap-free emulsion polymerization, a polymerization initiator is usually used. The polymerization initiator used may be any polymerization initiator that is soluble in the aqueous medium used in the polymerization, and potassium persulfate and ammonium persulfate are preferred. The amount of the polymerization initiator used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the monomer used in the soap-free emulsion polymerization. As the aqueous medium, any of the aqueous medium (D) described later can be used.
乳化重合によりシード粒子を含有する懸濁液を調製する場合には、通常、乳化剤および重合開始剤を使用する。使用される乳化剤の例としては、ドデシルベンゼンスルホン酸ナトリウムなどのアルキルベンゼンスルホン酸塩、ポリエチレングリコールノニルフェニルエーテルなどのポリエチレングリコールアルキルエーテルなどを挙げることができる。乳化剤は、モノマー１００重量部に対して０．０１〜５重量部の範囲で使用するのが好ましい。 When preparing a suspension containing seed particles by emulsion polymerization, an emulsifier and a polymerization initiator are usually used. Examples of the emulsifier used include alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, polyethylene glycol alkyl ethers such as polyethylene glycol nonyl phenyl ether, and the like. The emulsifier is preferably used in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer.
また、使用される重合開始剤としては、重合の際に使用される水性媒体に可溶な重合開始剤であればよく、好ましいのは、過硫酸カリウム、過硫酸アンモニウムである。重合開始剤の使用量は、ソープフリー乳化重合の際に使用される上記モノマー１００重量部に対して、０．１〜１０重量部の範囲が好ましい。また、水性媒体は、後記する水性媒体（Ｄ）をいずれも用いることができる。 The polymerization initiator used may be any polymerization initiator that is soluble in the aqueous medium used in the polymerization, and potassium persulfate and ammonium persulfate are preferred. The amount of the polymerization initiator used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the monomer used in the soap-free emulsion polymerization. As the aqueous medium, any of the aqueous medium (D) described later can be used.
前記の方法により調製されたシード粒子は、平均粒子径が０．０５〜２．０μｍ、好ましくは０．２〜０．６μｍであり、粒子径の相対標準偏差（以下、ＣＶ値と略記する）が、１０％以下の真球状単分散粒子であるのが好ましい。また、本発明では、前記のようにして調製した粒子径の小さいシード粒子をそのまま用いてもよいが、粒子径の小さいシード粒子にモノマーを吸収させ、吸収されたモノマーを重合させる、シード粒子重合を１回以上行い、粒子径の大きいシード粒子を調製して用いてもよい。 The seed particles prepared by the above method have an average particle diameter of 0.05 to 2.0 μm, preferably 0.2 to 0.6 μm, and a relative standard deviation of the particle diameter (hereinafter abbreviated as CV value). Is preferably 10% or less of true spherical monodisperse particles. In the present invention, seed particles having a small particle diameter prepared as described above may be used as they are. However, seed particles having a small particle diameter are allowed to absorb a monomer and polymerize the absorbed monomer. May be performed once or more to prepare seed particles having a large particle diameter.
粒子径の大きなシード粒子を調製するシード重合は、水性媒体に、前記の粒子径の小さいシード粒子、モノマーおよび重合開始剤、さらに必要により乳化剤および分散安定剤を配合して行うことができる。シード粒子重合で用いるモノマーとしては、粒子径の小さいシード粒子を構成する前記の（メタ）アクリル酸アルキルエステル、必要に応じて（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマーを用いることができる。用いるモノマーは、粒子径の小さいシード粒子を構成するモノマーと同一であっても異なっていてもよい。また、用いる重合開始剤の例としては、過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩、過酸化ベンゾイル、過酸化ラウリルなどの過酸化物、アゾビスイソブチロニトリルなどのアゾ化合物が挙げられる。重合開始剤は、単独でも２種以上組み合わせて使用してもよく、（メタ）アクリル酸アルキルエステル１００重量部に対して、０．１〜１０重量部の範囲で使用するのが好ましい。さらに、乳化剤および分散安定剤は、後記する乳化剤（Ｅ）および分散安定剤（Ｆ）のいずれも使用することができる。 Seed polymerization for preparing seed particles having a large particle size can be carried out by blending the above-mentioned seed particles having a small particle size, a monomer and a polymerization initiator, and, if necessary, an emulsifier and a dispersion stabilizer in an aqueous medium. As a monomer used in seed particle polymerization, the above-mentioned (meth) acrylic acid alkyl ester constituting a seed particle having a small particle diameter, and other monomers copolymerizable with (meth) acrylic acid alkyl ester, if necessary, are used. Can do. The monomer to be used may be the same as or different from the monomer constituting the seed particle having a small particle diameter. Examples of the polymerization initiator to be used include persulfates such as potassium persulfate and ammonium persulfate, peroxides such as benzoyl peroxide and lauryl peroxide, and azo compounds such as azobisisobutyronitrile. A polymerization initiator may be used individually or in combination of 2 or more types, It is preferable to use in 0.1-10 weight part with respect to 100 weight part of (meth) acrylic-acid alkylester. Further, as the emulsifier and the dispersion stabilizer, any of the emulsifier (E) and the dispersion stabilizer (F) described later can be used.
シード粒子の調製では、所望の粒子径のシード粒子を得るため、前記のシード重合を繰返して行ってもよく、通常１〜１０回、好ましくは１〜５回行う。所望の粒子径を有するシード粒子は、たとえば、ソープフリー乳化重合などの１段階目の重合で調製した粒子径の小さいシード粒子を使用してモノマーを吸収させ、吸収されたモノマーを重合するシード重合（２段階目の重合）を行い、必要であれば、その後さらに同様のシード重合を繰返すことにより、調製することができる。最終的に得られるシード粒子の平均粒子径は、０．７〜５．０μｍの範囲が好ましい。また、最終的に得られるシード粒子の重量は、１段階目の重合で調製した粒子径の小さいシード粒子の２〜８０倍、できれば５〜４０倍、とりわけ１０〜３０倍の範囲が好ましい。 In preparing the seed particles, the seed polymerization may be repeated in order to obtain seed particles having a desired particle diameter, and is usually performed 1 to 10 times, preferably 1 to 5 times. For seed particles having a desired particle diameter, for example, seed polymerization using a small particle diameter prepared in the first stage polymerization such as soap-free emulsion polymerization is used to absorb the monomer, and the absorbed monomer is polymerized. (Second-stage polymerization) is performed, and if necessary, the same seed polymerization is further repeated thereafter. The average particle diameter of the seed particles finally obtained is preferably in the range of 0.7 to 5.0 μm. The weight of the seed particles finally obtained is preferably in the range of 2 to 80 times, preferably 5 to 40 times, particularly 10 to 30 times that of the seed particles having a small particle diameter prepared by the first stage polymerization.
上記した重合方法により調製された（Ｂ）成分は、ゲル分率が１０〜８５％、ゾル分の重量平均分子量（以下、Ｍｗと略記する）が、１００，０００〜１，０００，０００であるのが好ましい。（Ｂ）成分のゲル分率が８５％を超えると、最終的に得られるアクリル粒子が所定の形状、特に中空形状になりにくいので好ましくない。また、ゾル分のＭｗが１００，０００〜１，０００，０００の範囲内であると、最終的に得られるアクリル粒子が所定の形状になりやすいので好ましい。なお、最終的に得られるアクリル粒子が所定の形状を形成するためには、（Ｂ）成分中のゾル分は、分子量が２００００以下のポリマーが少ないものが好ましい。ゲル分率あるいはＭｗは、用いるモノマーの種類・組み合わせ・割合、重合開始剤の種類・配合量、乳化剤の種類・配合量、および重合の方法・条件などにより調整できる。たとえば、（Ｂ）成分のゲル分率は、不飽和二重結合を２個以上有するモノマーの種類および配合量などにより調整できる。また、ゾル分のＭｗは、連鎖移動剤の種類・配合量、重合開始剤の種類・配合量、および重合の条件などにより調整できる。 The component (B) prepared by the polymerization method described above has a gel fraction of 10 to 85% and a weight average molecular weight of sol (hereinafter abbreviated as Mw) of 100,000 to 1,000,000. Is preferred. When the gel fraction of the component (B) exceeds 85%, it is not preferable because the finally obtained acrylic particles are unlikely to have a predetermined shape, particularly a hollow shape. Further, it is preferable that the Mw of the sol is in the range of 100,000 to 1,000,000 because the finally obtained acrylic particles are likely to have a predetermined shape. In order for the finally obtained acrylic particles to have a predetermined shape, the sol content in the component (B) is preferably a polymer having a small molecular weight of 20000 or less. The gel fraction or Mw can be adjusted by the type / combination / ratio of the monomers used, the type / blending amount of the polymerization initiator, the type / blending amount of the emulsifier, and the polymerization method / condition. For example, the gel fraction of the component (B) can be adjusted by the type and blending amount of the monomer having two or more unsaturated double bonds. Further, the Mw of the sol can be adjusted by the kind and blending amount of the chain transfer agent, the kind and blending amount of the polymerization initiator, and the polymerization conditions.
なお、本発明において、（Ｂ）成分のゲル分率は、試料約０．１ｇを秤量し、これを約５０ｍｌの酢酸エチル中に室温で１週間浸漬した後、溶剤不溶分を取り出し、１３０℃で約１時間乾燥して酢酸エチルを蒸発させた後に秤量し、次式より算出した。 In the present invention, the gel fraction of the component (B) was measured by weighing about 0.1 g of a sample and immersing it in about 50 ml of ethyl acetate at room temperature for 1 week, taking out the solvent-insoluble content, And dried for about 1 hour to evaporate ethyl acetate, and weighed and calculated from the following equation.
ゲル分率（重量％）＝（浸漬・乾燥後の不揮発成分の重量）／試料の重量×１００
また、本発明において、（Ｂ）成分中のゾル分のＭｗは、試料約０．１ｇを精秤し、これを約５０ｍｌの酢酸エチル中に室温で１週間浸漬したのち、不溶分とゾル分を溶解した酢酸エチル溶液とに分離し、ゾル分を溶解した酢酸エチル溶液を３０℃で減圧乾燥して酢酸エチルを除去し、示差屈折計（東ソー社製、型式：ＨＬＣ−８１２０、カラム：ＨＸＬ−Ｈ、Ｇ７０００ＨＸＬ、ＧＭＨＸＬ−Ｌ、Ｇ２５００ＨＸＬ）を用いて、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）により測定された標準ポリスチレン換算の分子量である。
重合開始剤（Ｃ）
本発明において（Ｃ）成分は、後記する製造方法において、（Ａ−１）成分および（Ａ−２）成分の共重合を開始させる役割を有する。本発明では、公知の重合開始剤を使用できるが、過酸化物、アゾ系化合物を使用することが好ましい。過酸化物の例としては、過硫酸カリウム、過硫酸アンモニウム、過酸化ベンゾイル、過酸化ラウロイル、ジアルキルパーエステルなどが挙げられる。Gel fraction (% by weight) = (weight of non-volatile components after immersion / drying) / weight of sample × 100
In the present invention, the Mw of the sol content in the component (B) is obtained by accurately weighing about 0.1 g of a sample and immersing it in about 50 ml of ethyl acetate at room temperature for 1 week, and then insoluble and sol content. The ethyl acetate solution in which the sol was dissolved was dried under reduced pressure at 30 ° C. to remove ethyl acetate, and a differential refractometer (Model: HLC-8120, manufactured by Tosoh Corporation, column: HXL) -H, G7000HXL, GMHXL-L, G2500HXL), and a molecular weight in terms of standard polystyrene measured by a gel permeation chromatography method (GPC method).
Polymerization initiator (C)
In the present invention, the component (C) has a role of initiating copolymerization of the components (A-1) and (A-2) in the production method described later. In the present invention, a known polymerization initiator can be used, but it is preferable to use a peroxide or an azo compound. Examples of peroxides include potassium persulfate, ammonium persulfate, benzoyl peroxide, lauroyl peroxide, and dialkyl peresters.
アゾ系化合物の例としては、２，２´−アゾビス（２−メチルプロピオニトリル）、２，２´−アゾビス（２−メチルブチロニトリル）、２，２´−アゾビス（２，４−ジメチルバレロニトリル）、２，２´−アゾビス（２−シクロプロピルプロピオニトリル）、１，１´−アゾビス（シクロヘキサン−１−カルボニトリル）、ジメチル−２，２´−アゾビス（２−メチルプロピオネート）などが挙げられる。これらの重合開始剤は、単独でも２種以上組み合わせて使用することができる。本発明での（Ｃ）成分の使用量は、（Ａ−１）成分と（Ａ−２）成分との合計１００重量部に対し、０．１〜１０重量部の範囲が好ましい。
水性媒体（Ｄ）
本発明において（Ｄ）成分は、水のほかに、水に親水性有機溶媒を添加した混合物でもよい。水としては、精製水（イオン交換水、蒸留水など）、地下水、水道水などが挙げられる。親水性有機溶媒の例としては、メタノール、エタノール、イソプロパノールなどの低級アルコール；エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、トリエチレングリコールなどの多価アルコール；メチルセロソルブ、エチルセロソルブなどのセロソルブ類：アセトンなどのケトン類；テトラヒドロフランなどのエーテル類；ギ酸メチルなどのエステル類などが挙げられる。これらの親水性有機溶媒は、単独でも２種以上組み合わせて使用することができる。親水性有機溶媒の添加量は、水１００重量部に対し、０．１〜１０重量部の範囲が好ましい。Examples of azo compounds include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethyl). Valeronitrile), 2,2′-azobis (2-cyclopropylpropionitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), dimethyl-2,2′-azobis (2-methylpropionate) ) And the like. These polymerization initiators can be used alone or in combination of two or more. The amount of component (C) used in the present invention is preferably in the range of 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of component (A-1) and component (A-2).
Aqueous medium (D)
In the present invention, the component (D) may be a mixture obtained by adding a hydrophilic organic solvent to water in addition to water. Examples of water include purified water (ion exchange water, distilled water, etc.), ground water, tap water and the like. Examples of hydrophilic organic solvents include: lower alcohols such as methanol, ethanol and isopropanol; polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, diethylene glycol and triethylene glycol; cellosolves such as methyl cellosolve and ethyl cellosolve: acetone Ketones such as; ethers such as tetrahydrofuran; esters such as methyl formate. These hydrophilic organic solvents can be used alone or in combination of two or more. The addition amount of the hydrophilic organic solvent is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of water.
本発明は、必要に応じて、上記水性媒体（Ｄ）に乳化剤（Ｅ）、分散安定剤（Ｆ）、および重合禁止剤（Ｇ）を含有させることができる。
乳化剤（Ｅ）
本発明において乳化剤（Ｅ）成分の例としては、ドデシルスルホン酸ナトリウムなどのアルキルスルホン酸塩；ドデシルベンゼンスルホン酸ナトリウムなどのアルキルベンゼンスルホン酸塩；２−スルホテトラデカン酸１−メチルエステルナトリウムなどのアルファスルホン脂肪酸エステル塩；ポリエチレングリコールノニルフェニルエーテルなどのポリエチレングリコールアルキルエーテル；ポリオキシエチレンアルキルエーテル、ポリオキシエチレン多環フェニルエーテル、アリルエーテルおよびそれらの硫酸エステルの塩；などを挙げることができ、これらの中では、ドデシルスルホン酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウムが好ましい。これらの乳化剤は、単独でも２種以上組み合わせて使用することができる。本発明での（Ｅ）成分の使用量は、（Ａ−１）成分と（Ａ−２）成分との合計１００重量部に対し、０．１〜１０重量部の範囲が好ましい。
分散安定剤（Ｆ）
本発明において分散安定材（Ｆ）成分の例としては、部分鹸化されたポリビニルアルコール；完全鹸化されたポリビニルアルコール；ポリアクリル酸、その共重合体およびこれらの中和物；ポリメタクリル酸、その共重合体およびこれらの中和物；カルボキシメチルセルロース、ヒドロキシプロピルメチルセルロースなどのセルロース類；ポリビニルピロリドンなどを挙げることができる。これらの分散安定剤は、単独でも２種以上組み合わせて使用することができる。本発明での（Ｆ）成分の使用量は、（Ａ−１）成分と（Ａ−２）成分との合計１００重量部に対し、０．１〜５重量部の範囲が好ましい。
重合禁止剤（Ｇ）
本発明において重合禁止剤（Ｇ）成分の例としては、亜硝酸ナトリウム、ヒドロキノン、ジブチルヒドロキシトルエンなどが挙げられる。これらの重合禁止剤は、単独でも２種以上組み合わせて使用することができる。本発明での（Ｇ）成分の使用量は、（Ｄ）成分中に０．０１〜０．５重量％の範囲で含有させるのが好ましい。
＜アクリル中空粒子の製造方法＞
本発明に係るアクリル中空粒子の製造方法について説明する。In the present invention, the aqueous medium (D) can contain an emulsifier (E), a dispersion stabilizer (F), and a polymerization inhibitor (G) as necessary.
Emulsifier (E)
Examples of the emulsifier (E) component in the present invention include alkyl sulfonates such as sodium dodecyl sulfonate; alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate; alpha sulfones such as 2-sulfotetradecanoic acid 1-methyl ester sodium. Fatty acid ester salts; polyethylene glycol alkyl ethers such as polyethylene glycol nonylphenyl ether; polyoxyethylene alkyl ethers, polyoxyethylene polycyclic phenyl ethers, allyl ethers and salts of their sulfates; Then, sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate are preferable. These emulsifiers can be used alone or in combination of two or more. The amount of the component (E) used in the present invention is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight as the total of the components (A-1) and (A-2).
Dispersion stabilizer (F)
Examples of the dispersion stabilizer (F) component in the present invention include: partially saponified polyvinyl alcohol; fully saponified polyvinyl alcohol; polyacrylic acid, its copolymer and neutralized product thereof; polymethacrylic acid, its co Examples thereof include polymers and neutralized products thereof; celluloses such as carboxymethylcellulose and hydroxypropylmethylcellulose; polyvinylpyrrolidone and the like. These dispersion stabilizers can be used alone or in combination of two or more. The amount of component (F) used in the present invention is preferably in the range of 0.1 to 5 parts by weight with respect to a total of 100 parts by weight of component (A-1) and component (A-2).
Polymerization inhibitor (G)
In the present invention, examples of the polymerization inhibitor (G) component include sodium nitrite, hydroquinone, dibutylhydroxytoluene and the like. These polymerization inhibitors can be used alone or in combination of two or more. The amount of component (G) used in the present invention is preferably contained in the component (D) in the range of 0.01 to 0.5% by weight.
<Method for producing acrylic hollow particles>
The manufacturing method of the acrylic hollow particle which concerns on this invention is demonstrated.
本発明では、まず、前記の（Ａ−１）成分、（Ａ−２）成分、（Ｃ）成分および（Ｄ）成分、必要に応じて（Ｅ）成分、（Ｆ）成分、（Ｇ）成分を混合、撹拌して水性分散液を調製する。（Ｄ）成分は、（Ａ−１）成分と（Ａ−２）成分との合計１００重量部に対し、８０〜５００重量部の範囲で投入することが好ましい。（Ａ−１）成分、（Ａ−２）成分、（Ｃ）成分および（Ｄ）成分を混合、撹拌して水性分散液を得る方法は、機械的せん断力を利用した公知の方法でよく、たとえば、ホモミキサー、ホモジナイザー、乳化分散機、超音波分散機などの装置を利用すればよい。混合・撹拌時の温度は、周囲からの熱により（Ｃ）成分が分解しない程度の温度以下であればよく、好ましいのは０〜３０℃である。また、本発明に係るアクリル中空粒子の製造方法では、疎水性有機溶剤を使用しないので、最終的に得られるアクリル中空粒子は、有機溶剤が残存しないので、粒子が脆くなりにくい。なお、疎水性有機溶剤とは、トルエン、酢酸エチル、ヘキサン、１−クロルドデカン、アジピン酸、ジオクチルなどの非重合性の有機溶剤を意味する。 In the present invention, first, the components (A-1), (A-2), (C) and (D), and (E), (F), and (G) as necessary. Are mixed and stirred to prepare an aqueous dispersion. The component (D) is preferably added in the range of 80 to 500 parts by weight with respect to 100 parts by weight as a total of the components (A-1) and (A-2). The method of obtaining an aqueous dispersion by mixing and stirring the components (A-1), (A-2), (C) and (D) may be a known method utilizing mechanical shearing force, For example, a device such as a homomixer, a homogenizer, an emulsifying disperser, or an ultrasonic disperser may be used. The temperature at the time of mixing and stirring should just be below the temperature of the grade which does not decompose | disassemble (C) component with the heat | fever from surroundings, and 0-30 degreeC is preferable. In the method for producing acrylic hollow particles according to the present invention, since a hydrophobic organic solvent is not used, since the organic solvent does not remain in the finally obtained acrylic hollow particles, the particles are not easily brittle. The hydrophobic organic solvent means a non-polymerizable organic solvent such as toluene, ethyl acetate, hexane, 1-chlorodecane, adipic acid, dioctyl and the like.
ついで、別途に調製した前記（Ｂ）成分によるシード粒子を、上記で得られた水性分散液に投入し、前記（Ｂ）成分によるシード粒子に前記（Ａ−１）成分、（Ａ−２）成分、（Ｃ）成分を吸収させる。（Ｂ）成分によるシード粒子の投入量は、（Ａ−１）成分と（Ａ−２）成分との合計１００重量部に対し、１．２５〜５０重量部の範囲で投入することが好ましい。 Next, seed particles based on the component (B) prepared separately are added to the aqueous dispersion obtained above, and the components (A-1) and (A-2) are added to the seed particles based on the component (B). The component (C) is absorbed. The amount of seed particles introduced by the component (B) is preferably in the range of 1.25 to 50 parts by weight with respect to a total of 100 parts by weight of the components (A-1) and (A-2).
ついで、（Ａ−１）成分および（Ａ−２）成分を吸収させた（Ｂ）成分を含有する水性分散液を加熱して、（Ａ−１）成分と（Ａ−２）成分とを共重合させることにより、アクリル中空粒子を製造することができる。このときの加熱温度は、５０〜９０℃の範囲に設定するのが好ましい。得られたアクリル中空粒子は、濾過、脱水など公知の方法で適宜水性分散液中より分離し、必要に応じて洗浄して製品化できる。
＜得られるアクリル中空粒子の形状＞
本発明において、得られるアクリル中空粒子は、中空であるコアと外殻であるシェルとを備え、シェルにはコアに通じる孔が２以上形成されている。本発明に係るアクリル中空粒子は、中実粒子より柔らかい感触を与え、コアに通じる孔が１しか形成されていない中空粒子より、吸油・吸水性および揮発成分の徐放性に優れているので、化粧料用のアクリル中空粒子として有用である。また、本発明に係るアクリル中空粒子の寸法は、以下のような要件を満たす。
シェルの外径（α）
本発明では、得られるアクリル中空粒子の平均粒子径、すなわちシェルの外径（α）は、３〜１０μｍであることを必須とする。シェルの外径（α）が３μｍ未満であると、目的とする中空の形状が得られず、しかも得られるアクリル中空粒子は、伸展性に劣り、べたつき感を与えるので、好ましくない。また、シェルの外径（α）が１０μｍを超えると、得られるアクリル中空粒子はしっとり感に劣るので好ましくない。シェルの外径（α）として好ましい範囲は、３．５〜８．０μｍである。
コアの径（β）
本発明では、得られるアクリル系中空粒子のコアの径（β）は、０．５〜８．５μｍであることが好ましい。コアの径（β）が０．５μｍ未満であると、粒子にソフト感が得られにくいので好ましくない。また、コアの径（β）が８．５μｍを超えると、粒子が脆くなり、使用感に劣るので好ましくない。コアの径（β）としてより好ましい範囲は、１．０〜８．０μｍである。Next, the aqueous dispersion containing the component (B) in which the component (A-1) and the component (A-2) are absorbed is heated so that the component (A-1) and the component (A-2) are combined. Acrylic hollow particles can be produced by polymerization. The heating temperature at this time is preferably set in the range of 50 to 90 ° C. The obtained acrylic hollow particles can be appropriately separated from the aqueous dispersion by a known method such as filtration and dehydration, and washed to obtain a product as necessary.
<Shape of the resulting acrylic hollow particles>
In the present invention, the resulting acrylic hollow particles include a hollow core and a shell that is an outer shell, and the shell has two or more holes leading to the core. The acrylic hollow particles according to the present invention give a softer feeling than the solid particles, and are superior in oil absorption / water absorption and sustained release of volatile components than hollow particles in which only one hole leading to the core is formed. It is useful as acrylic hollow particles for cosmetics. Moreover, the dimension of the acrylic hollow particle which concerns on this invention satisfy | fills the following requirements.
Shell outer diameter (α)
In the present invention, it is essential that the average particle diameter of the resulting acrylic hollow particles, that is, the outer diameter (α) of the shell is 3 to 10 μm. When the outer diameter (α) of the shell is less than 3 μm, the intended hollow shape cannot be obtained, and the resulting acrylic hollow particles are inferior in extensibility and give a sticky feeling, which is not preferable. On the other hand, when the outer diameter (α) of the shell exceeds 10 μm, the resulting acrylic hollow particles are not preferable because they are inferior in moist feeling. A preferred range for the outer diameter (α) of the shell is 3.5 to 8.0 μm.
Core diameter (β)
In the present invention, the diameter (β) of the core of the acrylic hollow particles obtained is preferably 0.5 to 8.5 μm. When the core diameter (β) is less than 0.5 μm, it is difficult to obtain a soft feeling in the particles, which is not preferable. On the other hand, if the core diameter (β) exceeds 8.5 μm, the particles become brittle, and the feeling of use is inferior. A more preferable range of the core diameter (β) is 1.0 to 8.0 μm.
本発明では、前記シェルの外径（α）と前記コアの径（β）との比｛（α）／（β）｝は、１．１〜３．５の範囲であることを必須とする。｛（α）／（β）｝が１．１未満であると、粒子が脆くなり、使用感に劣るので好ましくない。また、｛（α）／（β）｝が３．５を超えると、粒子にソフト感が得られにくいので好ましくない。｛（α）／（β）｝で好ましい範囲は、１．１〜３．５である。
コアに通じる孔の最大の孔の径（γ）
本発明では、得られるアクリル中空粒子に形成されたコアに通じる２以上の孔のうち、最大の孔の径（γ）が、０．３〜２．５μｍであることを必須とする。最大の孔の径（γ）が０．３〜２．５μｍの範囲内であると、吸油・吸水性および揮発成分の徐放性に優れ、化粧料用のアクリル中空粒子として有用であるので好ましい。最大の孔の径（γ）として好ましい範囲は、０．４〜１．６μｍである。In the present invention, it is essential that the ratio {(α) / (β)} of the outer diameter (α) of the shell and the diameter (β) of the core is in the range of 1.1 to 3.5. . It is not preferred that {(α) / (β)} is less than 1.1 because the particles become brittle and inferior in usability. Moreover, it is not preferable that {(α) / (β)} exceeds 3.5 because it is difficult to obtain a soft feeling in the particles. A preferable range of {(α) / (β)} is 1.1 to 3.5.
Diameter of the largest hole leading to the core (γ)
In the present invention, it is essential that the diameter (γ) of the largest hole among the two or more holes leading to the core formed in the resulting acrylic hollow particle is 0.3 to 2.5 μm. When the maximum pore diameter (γ) is in the range of 0.3 to 2.5 μm, it is excellent in oil absorption / water absorption and sustained release of volatile components, and is useful as acrylic hollow particles for cosmetics. . A preferable range for the maximum hole diameter (γ) is 0.4 to 1.6 μm.
本発明では、前記コアの径（β）と前記最大の孔の径（γ）との比｛（β）／（γ）｝は、１．１〜２５．０の範囲であることを必須とする。｛（β）／（γ）｝が１．１〜２５．０の範囲内にあると、吸油・吸水性および揮発成分の徐放性に優れ、化粧料用のアクリル粒子として有用であるので好ましい。｛（β）／（γ）｝で好ましい範囲は、１．１５〜２４．０である。 In the present invention, it is essential that the ratio {(β) / (γ)} of the core diameter (β) to the maximum hole diameter (γ) is in the range of 1.1 to 25.0. To do. It is preferable that {(β) / (γ)} is in the range of 1.1 to 25.0 because it is excellent in oil absorption / water absorption and sustained release of volatile components and is useful as acrylic particles for cosmetics. . A preferable range of {(β) / (γ)} is 1.15 to 24.0.
本発明において、アクリル中空粒子の寸法｛（α）、（β）、（γ）｝は、次の方法により測定している。
（Ｉ）得られたアクリル中空粒子を未反応のエポキシ樹脂に添加し、包埋させる。
（ＩＩ）ついで、２３℃６５％ＲＨの環境下で放置し、エポキシ樹脂を硬化させる。
（ＩＩＩ）ついで、硬化したエポキシ樹脂を凍結させる。
（ＩＶ）凍結したエポキシ樹脂をダイヤモンドナイフまたはガラスナイフで断面出しを行い、測定用試料を作製する。
（ＶＩ）ついで、作製した測定用試料を、走査型電子顕微鏡（以下、ＳＥＭと略記する）を使用して、シェルの外径（α）、コアの径（β）、およびコアに通じる最大の孔の径（γ）を測定し、測定した各１０個の平均値を算出した。In the present invention, the dimensions {(α), (β), (γ)} of the acrylic hollow particles are measured by the following method.
(I) The obtained acrylic hollow particles are added to an unreacted epoxy resin and embedded.
(II) Next, it is left in an environment of 23 ° C. and 65% RH to cure the epoxy resin.
(III) Next, the cured epoxy resin is frozen.
(IV) The frozen epoxy resin is sectioned with a diamond knife or a glass knife to prepare a measurement sample.
(VI) Next, using the scanning electron microscope (hereinafter abbreviated as SEM), the outer diameter of the shell (α), the diameter of the core (β), and the maximum that leads to the core are measured. The diameter (γ) of the holes was measured, and the average value of each 10 measured was calculated.
本発明に係るアクリル中空粒子は、化粧料、複合粒子、インキ添加剤、潤滑油添加剤、焼結体、積層接着剤などに用いられ、とりわけ化粧料用の配合成分として好適に用いられる。化粧料としては、整髪料、毛髪料、頭皮料、毛髪着色料、洗髪料、ヘアリンスなどの頭髪用化粧料；化粧水、化粧液、クリーム、乳液、洗顔料、フェイシャルリンス、パック、化粧用油などの皮膚用化粧料；ファンデーション、化粧下地、おしろい、口紅、ボディパウダー、アイシャドウ、眉墨、頬紅、ネイルエナメル、除光液などの仕上げ用化粧料；ならびに香水、オーデコロン、バスオイル、ベビーオイル、ベビーパウダー、ベビーローションなどが挙げられる。また、アクリル中空粒子は、化粧料に配合する前に、薬剤などの有効成分を配合させることができる。 The acrylic hollow particles according to the present invention are used in cosmetics, composite particles, ink additives, lubricating oil additives, sintered bodies, laminating adhesives, and the like, and are particularly suitably used as cosmetic ingredients. As cosmetics, hair cosmetics such as hairdressing, hair, scalp, hair coloring, hair washing, hair rinse, etc .; lotion, lotion, cream, milky lotion, facial cleanser, facial rinse, pack, cosmetic oil Cosmetics for skin such as foundations, makeup bases, funny, lipsticks, body powders, eye shadows, eyebrows, blushers, nail enamels, and light removal solutions; and perfumes, cologne, bath oil, baby oil, Examples include baby powder and baby lotion. In addition, the acrylic hollow particles can be blended with an active ingredient such as a drug before blending into the cosmetic.
本発明を実施例に基づいてさらに具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例によって限定されることはない。
［製造例１：シード粒子の調製］
（１段階目の重合：ソープフリー乳化重合）
温度計と窒素導入管とを装着した容量１リットルの四つ口フラスコに、メチルメタクリレート（以下、ＭＭＡと略記する）１００重量部、およびイオン交換水３００重量部を投入して混合撹拌し、さらに窒素気流下で撹拌を行いながら８０℃に昇温した。The present invention will be described more specifically based on examples, but the present invention is not limited by the following examples unless it exceeds the gist.
[Production Example 1: Preparation of seed particles]
(First stage polymerization: soap-free emulsion polymerization)
100 parts by weight of methyl methacrylate (hereinafter abbreviated as MMA) and 300 parts by weight of ion-exchanged water are added to a 1-liter four-necked flask equipped with a thermometer and a nitrogen introduction tube, and mixed and stirred. The temperature was raised to 80 ° C. while stirring under a nitrogen stream.
ついで、加温された混合液中に過硫酸カリウム０．５重量部を加え、８０℃に保持しながら６時間反応させ、（メタ）アクリル系ポリマー粒子の分散液（ア）を得た。分散液（ア）中の（メタ）アクリル系ポリマー粒子をＳＥＭ（日立ハイテクノロジーズ社製、型式：Ｓ−４８００、以下同じ）により観察したところ、この（メタ）アクリル系ポリマー粒子は、平均粒子径０．４μｍ、ＣＶ値２．０％である、真球状の単分散粒子であった。また、分散液（ア）中の固形分量は２４重量％であった。
（２段階目の重合：シード重合）
同様の装置において、ＭＭＡ１００重量部、エチレングリコールジメタクリレート（以下、ＥＧＤＭＡと略記する）０．０２重量部、過酸化ベンゾイル１．０重量部、イオン交換水１１３．２重量部、ドデシルベンゼンスルホン酸ナトリウム０．５重量部、および硝酸ナトリウム０．１重量部を投入して混合撹拌し、混合液を得た。Next, 0.5 part by weight of potassium persulfate was added to the heated mixture and reacted for 6 hours while maintaining at 80 ° C. to obtain a dispersion (a) of (meth) acrylic polymer particles. When the (meth) acrylic polymer particles in the dispersion liquid (a) were observed by SEM (manufactured by Hitachi High-Technologies Corporation, model: S-4800, the same shall apply hereinafter), the (meth) acrylic polymer particles had an average particle diameter. It was a true spherical monodisperse particle having 0.4 μm and a CV value of 2.0%. Further, the solid content in the dispersion (a) was 24% by weight.
(Second stage polymerization: seed polymerization)
In the same apparatus, 100 parts by weight of MMA, 0.02 parts by weight of ethylene glycol dimethacrylate (hereinafter abbreviated as EGDMA), 1.0 part by weight of benzoyl peroxide, 113.2 parts by weight of ion-exchanged water, sodium dodecylbenzenesulfonate 0.5 parts by weight and 0.1 parts by weight of sodium nitrate were added and mixed and stirred to obtain a mixed solution.
ついで、この混合液に、１段階目の重合で得た分散液（ア）６４．２重量部、部分鹸化されたポリビニルアルコール（クラレ社製、品番名：ＰＶ−４２０）をイオン交換水で５％に溶解した水溶液（以下、ＰＶＡ５％水溶液と略記する）４０重量部を添加し、穏やかに撹拌したあと、７５℃で２時間撹拌して、（メタ）アクリル系ポリマー粒子の分散液（イ）を得た。分散液（イ）中の（メタ）アクリル系ポリマー粒子をＳＥＭにより観察したところ、この（メタ）アクリル系ポリマー粒子は、平均粒子径０．７５μｍ、ＣＶ値２．５％である、真球状の単分散粒子であった。また、分散液（イ）中の固形分量は３０．５重量％であった。
（３段階目の重合：シード重合）
さらに、同様の装置において、ブチルアクリレート（以下、ＢＡと略記する）５．４重量部、ＭＭＡ９４．６重量部、ＥＧＤＭＡ０．０２２重量部、過酸化ベンゾイル１．１重量部、イオン交換水１４４．３重量部、ドデシルベンゼンスルホン酸ナトリウム０．５５重量部、および亜硝酸ナトリウム０．１１重量部を投入して混合撹拌し、混合液を得た。Next, 64.2 parts by weight of the dispersion liquid (a) obtained by the first-stage polymerization, 5 parts of partially saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., product number: PV-420) was added to this mixed liquid with ion-exchanged water. 40 parts by weight of an aqueous solution (hereinafter abbreviated as 5% PVA aqueous solution) was added and stirred gently, and then stirred at 75 ° C. for 2 hours to obtain a dispersion of (meth) acrylic polymer particles (A) Got. When the (meth) acrylic polymer particles in the dispersion (I) were observed by SEM, the (meth) acrylic polymer particles had a spherical shape with an average particle diameter of 0.75 μm and a CV value of 2.5%. Monodispersed particles. Further, the solid content in the dispersion (i) was 30.5% by weight.
(3rd stage polymerization: seed polymerization)
Further, in the same apparatus, 5.4 parts by weight of butyl acrylate (hereinafter abbreviated as BA), 94.6 parts by weight of MMA, 0.022 parts by weight of EGDMA, 1.1 parts by weight of benzoyl peroxide, 144.3 ion-exchanged water Part by weight, 0.55 part by weight of sodium dodecylbenzenesulfonate, and 0.11 part by weight of sodium nitrite were added and mixed and stirred to obtain a mixed solution.
ついで、この混合液に、２段階目の重合で得た分散液（イ）２７．３重量部、ＰＶＡ５％水溶液４３．３重量部を添加し、穏やかに撹拌したあと、７５℃で２時間撹拌して、(メタ)アクリル系ポリマー粒子の分散液（ウ）を得た。 Next, 27.3 parts by weight of the dispersion (ii) obtained in the second stage polymerization and 43.3 parts by weight of a PVA 5% aqueous solution were added to this mixed solution, and the mixture was gently stirred and then stirred at 75 ° C. for 2 hours. As a result, a dispersion (C) of (meth) acrylic polymer particles was obtained.
分散液（ウ）中の（メタ）アクリル系ポリマー粒子をＳＥＭにより観察したところ、この（メタ）アクリル系ポリマー粒子は、平均粒子径１．７μｍ、ＣＶ値２．５％である、真球状の単分散粒子であった。また、この分散液（ウ）中の固形分量は３０．１重量％であり、得られた（メタ）アクリル系ポリマーのゲル分率は６５％、ゾル分のＭｗは４００，０００であった。 When the (meth) acrylic polymer particles in the dispersion liquid (c) were observed by SEM, the (meth) acrylic polymer particles had an average particle diameter of 1.7 μm and a CV value of 2.5%. Monodispersed particles. Further, the solid content in this dispersion (c) was 30.1% by weight, the gel fraction of the obtained (meth) acrylic polymer was 65%, and the Mw of the sol was 400,000.
なお、（Ｂ）成分のゲル分率は、試料約０．１ｇを秤量し、これを約５０mlの酢酸エチル中に室温で１週間浸漬した後、溶剤不溶分を取り出し、１３０℃で約１時間乾燥して酢酸エチルを蒸発させた後に秤量し、次式より算出した。 As for the gel fraction of component (B), about 0.1 g of a sample was weighed and immersed in about 50 ml of ethyl acetate at room temperature for 1 week, and then the solvent-insoluble matter was taken out and about 130 hours at 130 ° C. After drying and evaporating ethyl acetate, it was weighed and calculated from the following equation.
ゲル分率（重量％）＝（浸漬・乾燥後の重量）／試料の重量×１００
また、シード粒子中のゾル分のＭｗは、試料約０．１ｇを精秤し、これを約５０mlの酢酸エチル中に室温で１週間浸漬したのち、不溶分とゾル分を溶解した酢酸エチル溶液とに分離し、ゾル分を溶解した酢酸エチル溶液を３０℃で減圧乾燥して酢酸エチルを除去し、示差屈折計（東ソー社製、型式：ＨＬＣ−８１２０、カラム：ＨＸＬ−Ｈ、Ｇ７０００ＨＸＬ、ＧＭＨＸＬ−Ｌ、Ｇ２５００ＨＸＬ）を用いて、ＧＰＣ法により測定された標準ポリスチレン換算の分子量である。
［製造例２：シード粒子の調製］
同様の装置において、ＭＭＡ１００重量部、ＥＧＤＭＡ０．０２５重量部、過酸化ベンゾイル１．０重量部、イオン交換水１４５．５重量部、ドデシルベンゼンスルホン酸ナトリウム０．６３重量部、および硝酸ナトリウム０．１３重量部を投入して混合撹拌し、混合液を得た。ついで、この混合液に、前記の分散液（ア）８２．０重量部、ＰＶＡ５％水溶液５０重量部を添加し、穏やかに撹拌したあと、７５℃で２時間撹拌して、（メタ）アクリル系ポリマー粒子の分散液（エ）を得た。分散液（エ）中の（メタ）アクリル系ポリマー粒子をＳＥＭにより観察したところ、この（メタ）アクリル系ポリマー粒子は、平均粒子径１．２８μｍ、ＣＶ値２．７％である、真球状の単分散粒子であった。また、分散液（エ）中の固形分量は３０．２重量％であり、得られた（メタ）アクリル系ポリマーのゲル分率は６０％、ゾル分のＭｗは３５０，０００であった。
［製造例３：シード粒子の調製］
同様の装置において、ＭＭＡ１００重量部、ＥＧＤＭＡ０．０２５重量部、過酸化ベンゾイル１．０重量部、イオン交換水１４５．５重量部、ドデシルベンゼンスルホン酸ナトリウム０．６３重量部、および硝酸ナトリウム０．１３重量部を投入して混合撹拌し、混合液を得た。ついで、この混合液に、前記の分散液（ウ）８２．０重量部、ＰＶＡ５％水溶液５０重量部を添加し、穏やかに撹拌したあと、７５℃で２時間撹拌して、（メタ）アクリル系ポリマー粒子の分散液（オ）を得た。分散液（オ）中の（メタ）アクリル系ポリマー粒子をＳＥＭにより観察したところ、この（メタ）アクリル系ポリマー粒子は、平均粒子径２．９μｍ、ＣＶ値３．２％である、真球状の単分散粒子であった。また、分散液（オ）中の固形分量は３０．２重量％であり、得られた（メタ）アクリル系ポリマー粒子のゲル分率は６０％、ゾル分のＭｗは３８０，０００であった。
［製造例４：シード粒子の調製］
同様の装置において、ＭＭＡ１００重量部、ノルマルドデシルメルカプタン１．０重量部、過酸化ベンゾイル２．０重量部、イオン交換水１４４．５重量部、ドデシルベンゼンスルホン酸ナトリウム０．５重量部、および亜硝酸ナトリウム０．１重量部を投入し、窒素気流下で混合撹拌して混合液を得た。ついで、この混合液に、前記の分散液（イ）２５．２重量部、ＰＶＡ５％水溶液４０重量部を添加し、穏やかに撹拌したあと、７５℃で２時間撹拌して、（メタ）アクリル系ポリマー粒子の分散液（カ）を得た。分散液（カ）中の（メタ）アクリル系ポリマー粒子をＳＥＭにより観察したところ、この（メタ）アクリル系ポリマー粒子は、平均粒子径１．７μｍ、ＣＶ値２．８％である、真球状の単分散粒子であった。また、分散液（カ）中の固形分量は３０．２重量％であり、得られた（メタ）アクリル系ポリマー粒子のゲル分率は０％、ゾル分のＭｗは５０，０００であった。
＜実施例１＞
ホモポリマーのＴｇが５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）として、
ＢＡを１１０重量部、
不飽和二重結合を２個以上有するモノマー（Ａ−２）として、ＥＧＤＭＡを８０重量部、
重合開始剤（Ｃ）として、過酸化ベンゾイルを２．０重量部、
水性媒体（Ｄ）として、イオン交換水を２６３重量部、
乳化剤（Ｅ）として、ドデシルベンゼンスルホン酸ナトリウムを１．０重量部、
および
重合禁止剤（Ｇ）として、亜硝酸ナトリウムを０．２重量部、
をホモミキサー（特殊機化工業社製、型式：ＴＫホモミキサーＭＡＲＫＩＩ、以下同じ）にて、１０，０００ｒｐｍで３分間撹拌した。Gel fraction (% by weight) = (weight after immersion / drying) / weight of sample × 100
The Mw of the sol in the seed particles is an ethyl acetate solution in which about 0.1 g of a sample is precisely weighed and immersed in about 50 ml of ethyl acetate for 1 week at room temperature, and then the insoluble and sol contents are dissolved. The ethyl acetate solution in which the sol was dissolved was dried under reduced pressure at 30 ° C. to remove ethyl acetate, and a differential refractometer (manufactured by Tosoh Corporation, model: HLC-8120, column: HXL-H, G7000HXL, GMHXL) -L, G2500HXL), and the molecular weight in terms of standard polystyrene measured by the GPC method.
[Production Example 2: Preparation of seed particles]
In the same apparatus, MMA 100 parts by weight, EGDMA 0.025 parts by weight, benzoyl peroxide 1.0 part by weight, ion-exchanged water 145.5 parts by weight, sodium dodecylbenzenesulfonate 0.63 parts by weight, and sodium nitrate 0.13 A part by weight was added and mixed and stirred to obtain a mixed solution. Next, 82.0 parts by weight of the above dispersion (A) and 50 parts by weight of a PVA 5% aqueous solution were added to this mixed solution, and after gently stirring, the mixture was stirred at 75 ° C. for 2 hours to obtain a (meth) acrylic system. A dispersion (D) of polymer particles was obtained. When the (meth) acrylic polymer particles in the dispersion liquid (d) were observed by SEM, the (meth) acrylic polymer particles had a true spherical shape with an average particle diameter of 1.28 μm and a CV value of 2.7%. Monodispersed particles. Further, the solid content in the dispersion (d) was 30.2% by weight, the gel fraction of the obtained (meth) acrylic polymer was 60%, and the Mw of the sol was 350,000.
[Production Example 3: Preparation of seed particles]
In the same apparatus, MMA 100 parts by weight, EGDMA 0.025 parts by weight, benzoyl peroxide 1.0 part by weight, ion-exchanged water 145.5 parts by weight, sodium dodecylbenzenesulfonate 0.63 parts by weight, and sodium nitrate 0.13 A part by weight was added and mixed and stirred to obtain a mixed solution. Next, 82.0 parts by weight of the above dispersion (c) and 50 parts by weight of a 5% PVA aqueous solution were added to this mixed liquid, and after gently stirring, the mixture was stirred at 75 ° C. for 2 hours to obtain a (meth) acrylic system. A dispersion (e) of polymer particles was obtained. When the (meth) acrylic polymer particles in the dispersion (e) were observed by SEM, the (meth) acrylic polymer particles had an average particle size of 2.9 μm and a CV value of 3.2%. Monodispersed particles. The solid content in the dispersion (e) was 30.2% by weight, the gel fraction of the (meth) acrylic polymer particles obtained was 60%, and the Mw of the sol was 380,000.
[Production Example 4: Preparation of seed particles]
In the same apparatus, 100 parts by weight of MMA, 1.0 part by weight of normal dodecyl mercaptan, 2.0 parts by weight of benzoyl peroxide, 144.5 parts by weight of ion-exchanged water, 0.5 part by weight of sodium dodecylbenzenesulfonate, and nitrous acid 0.1 part by weight of sodium was added and mixed and stirred under a nitrogen stream to obtain a mixed solution. Next, 25.2 parts by weight of the above dispersion (ii) and 40 parts by weight of a PVA 5% aqueous solution were added to this mixed solution, and after gently stirring, the mixture was stirred at 75 ° C. for 2 hours to obtain a (meth) acrylic system. A dispersion (F) of polymer particles was obtained. When the (meth) acrylic polymer particles in the dispersion liquid (f) were observed by SEM, the (meth) acrylic polymer particles had a spherical shape with an average particle diameter of 1.7 μm and a CV value of 2.8%. Monodispersed particles. Further, the solid content in the dispersion (f) was 30.2% by weight, the gel fraction of the obtained (meth) acrylic polymer particles was 0%, and the Mw of the sol was 50,000.
<Example 1>
As a non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a Tg of homopolymer of 50 ° C. or less,
110 parts by weight of BA,
As a monomer (A-2) having two or more unsaturated double bonds, 80 parts by weight of EGDMA,
As a polymerization initiator (C), 2.0 parts by weight of benzoyl peroxide,
As an aqueous medium (D), 263 parts by weight of ion-exchanged water,
As an emulsifier (E), 1.0 part by weight of sodium dodecylbenzenesulfonate,
And 0.2 parts by weight of sodium nitrite as a polymerization inhibitor (G),
Was stirred at 10,000 rpm for 3 minutes with a homomixer (made by Tokushu Kika Kogyo Co., Ltd., model: TK homomixer MARKII, hereinafter the same).
ついで、この混合物に、前記の製造例１で調製した分散液（ウ）を３３．２重量部添加し、５０℃で３０分間穏やかに撹拌した。その後、分散安定剤（Ｆ）として、ＰＶＡ５％水溶液を１２０重量部添加し、７５℃で１．５時間反応させ、つづいて９０℃で１時間反応させた。ついで、得られた水性分散液をブフナーロートで濾紙による減圧ろ過をし、そのケーキを１０５℃に設定した熱風乾燥機にて乾燥してアクリル中空粒子を得た。得られたアクリル中空粒子を下記の方法によって寸法測定、特性評価を行い、その結果を表１および表２に示した。
＜実施例２〜実施例３、比較例１〜比較例２＞
（Ａ−１）、（Ａ−２）を表１に示した割合にした以外は、実施例１と同様の方法でアクリル中空粒子を得た。得られたアクリル中空粒子を下記の方法によって寸法測定、特性評価を行い、その結果を表１および表２に示した。
＜実施例４＞
分散液（ウ）を３３．２重量部添加する代わりに、分散液（エ）を３３．２重量部添加した以外は、実施例１と同様の方法でアクリル中空粒子を調製した。得られたアクリル中空粒子を下記の方法によって寸法測定、特性評価を行い、その結果を表１および表２に示した。
＜実施例５＞
分散液（ウ）を３３．２重量部添加する代わりに、分散液（オ）を３３．２重量部添加した以外は、実施例１と同様の方法でアクリル粒子を調製した。得られたアクリル粒子を下記の方法によって寸法測定、特性評価を行い、その結果を表１および表２に示した。
＜実施例６＞
（Ａ−１）としてｎ−ブチルメタクリレートを１１０重量部投入した以外は、実施例１と同様の方法でアクリル中空粒子を得た。得られたアクリル中空粒子を下記の方法によって寸法測定、特性評価を行い、その結果を表１および表２に示した。
＜比較例３＞
分散液（ウ）を３３．２重量部添加する代わりに、分散液（カ）を３３．２重量部添加した以外は、実施例１と同様の方法で、アクリル粒子を調製した。得られたアクリル粒子を下記の方法によって寸法測定、特性評価を行い、その結果を表１および表２に示した。
＜比較例４＞
ホモポリマーのＴｇが５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）として、
ＢＡを１００重量部、
不飽和二重結合を２個以上有するモノマー（Ａ−２）として、１，６−ヘキサンジオールジメタクリレートを５０重量部、
疎水性有機溶剤として、ｎ−ヘキサンを１５０重量部、
重合開始剤（Ｃ）として、過酸化ベンゾイルを１．０重量部、
水性媒体（Ｄ）として、イオン交換水を７４４重量部、
乳化剤（Ｅ）として、ラリウル硫酸ナトリウムを０．１２重量部、
分散安定剤（Ｆ）として、ＰＶＡ５％水溶液を４８０重量部
および
重合禁止剤（Ｇ）として、亜硝酸ナトリウムを０．１重量部、
をホモミキサーにて、６，５００ｒｐｍで３分間撹拌し、分散液を得た。Next, 33.2 parts by weight of the dispersion liquid (c) prepared in Production Example 1 was added to this mixture and gently stirred at 50 ° C. for 30 minutes. Thereafter, 120 parts by weight of a 5% PVA aqueous solution was added as a dispersion stabilizer (F) and reacted at 75 ° C. for 1.5 hours, followed by reaction at 90 ° C. for 1 hour. Subsequently, the obtained aqueous dispersion was filtered under reduced pressure using a filter paper with a Buchner funnel, and the cake was dried with a hot air dryer set at 105 ° C. to obtain acrylic hollow particles. The obtained acrylic hollow particles were subjected to dimensional measurement and characteristic evaluation by the following methods, and the results are shown in Tables 1 and 2.
<Example 2 to Example 3, Comparative Example 1 to Comparative Example 2>
Acrylic hollow particles were obtained in the same manner as in Example 1 except that (A-1) and (A-2) were changed to the ratios shown in Table 1. The obtained acrylic hollow particles were subjected to dimensional measurement and characteristic evaluation by the following methods, and the results are shown in Tables 1 and 2.
<Example 4>
Acrylic hollow particles were prepared in the same manner as in Example 1 except that 33.2 parts by weight of the dispersion liquid (d) was added instead of 33.2 parts by weight of the dispersion liquid (c). The obtained acrylic hollow particles were subjected to dimensional measurement and characteristic evaluation by the following methods, and the results are shown in Tables 1 and 2.
<Example 5>
Acrylic particles were prepared in the same manner as in Example 1 except that 33.2 parts by weight of the dispersion liquid (v) was added instead of 33.2 parts by weight of the dispersion liquid (c). The obtained acrylic particles were subjected to dimensional measurement and characteristic evaluation by the following methods, and the results are shown in Tables 1 and 2.
<Example 6>
Acrylic hollow particles were obtained in the same manner as in Example 1 except that 110 parts by weight of n-butyl methacrylate was added as (A-1). The obtained acrylic hollow particles were subjected to dimensional measurement and characteristic evaluation by the following methods, and the results are shown in Tables 1 and 2.
<Comparative Example 3>
Acrylic particles were prepared in the same manner as in Example 1 except that 33.2 parts by weight of the dispersion (F) was added instead of adding 33.2 parts by weight of the dispersion (C). The obtained acrylic particles were subjected to dimensional measurement and characteristic evaluation by the following methods, and the results are shown in Tables 1 and 2.
<Comparative example 4>
As a non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a Tg of homopolymer of 50 ° C. or less,
100 parts by weight of BA,
As a monomer (A-2) having two or more unsaturated double bonds, 50 parts by weight of 1,6-hexanediol dimethacrylate,
As a hydrophobic organic solvent, 150 parts by weight of n-hexane,
As a polymerization initiator (C), 1.0 part by weight of benzoyl peroxide,
As the aqueous medium (D), 744 parts by weight of ion-exchanged water,
As an emulsifier (E), 0.12 parts by weight of sodium lauryl sulfate,
As dispersion stabilizer (F), 480 parts by weight of PVA 5% aqueous solution and as polymerization inhibitor (G), 0.1 part by weight of sodium nitrite,
Was stirred with a homomixer at 6,500 rpm for 3 minutes to obtain a dispersion.
ついで、この分散液を、撹拌機および温度計を備えた重合反応器に入れ、６０℃に保持しながら６時間撹拌を続けて懸濁重合を行った。この懸濁液をろ過し、得られた反応生成物を洗浄、乾燥、粉砕して、平均粒子径５．５μｍの球状多孔質樹脂微粒子を得た。ついで、得られた水性分散液をブフナーロートで濾紙による減圧ろ過をし、そのケーキを１０５℃に設定した熱風乾燥機にて乾燥してアクリル多孔質粒子を得た。得られたアクリル多孔質粒子を下記の方法によって寸法測定、特性評価を行い、その結果を表１および表２に示した。
＜比較例５＞
市販のナイロン粒子を下記の方法によって寸法測定、特性評価を行い、その結果を表２に示した。
［寸法測定］
上記の方法で調製したアクリル中空粒子、およびナイロン粒子を、エポキシ樹脂｛Struers社製のSpeci Fix ResinとSpeci Fix―２０Curing Agentとを７：１（重量比）の割合で混練した混合物｝に混合させて、２３℃６５％ＲＨの環境下で２４時間放置した。硬化した板状のエポキシ樹脂を−３０℃の条件下で１時間静置した後、ウルトラミクロトームの内部に（Ｌｅｉｃａ社製、型式名：ＥＭＵＣ６）の内部にガラスナイフで断面出しを行い、測定用試料を作製した。ついで、作製した試料を、ＳＥＭを使用して、シェルの外径（α）、コアの径（β）、中空粒子については、さらにコアに通じる最大の孔の径（γ）を測定し、測定した各１０個の粒子の平均値を算出した（単位［μｍ］）。
［特性評価］
アクリル中空粒子およびナイロン粒子は、次に記載の方法で特性評価を行った。Subsequently, this dispersion was put into a polymerization reactor equipped with a stirrer and a thermometer, and stirred for 6 hours while maintaining the temperature at 60 ° C. to carry out suspension polymerization. This suspension was filtered, and the resulting reaction product was washed, dried and pulverized to obtain spherical porous resin fine particles having an average particle size of 5.5 μm. Next, the obtained aqueous dispersion was filtered under reduced pressure using a Buchner funnel with a filter paper, and the cake was dried with a hot air dryer set at 105 ° C. to obtain acrylic porous particles. The obtained acrylic porous particles were subjected to dimensional measurement and characteristic evaluation by the following methods, and the results are shown in Tables 1 and 2.
<Comparative Example 5>
The commercially available nylon particles were dimensionally measured and characterized by the following methods, and the results are shown in Table 2.
[Dimension measurement]
The acrylic hollow particles and nylon particles prepared by the above method are mixed in an epoxy resin {a mixture obtained by kneading Speci Fix Resin and Speci Fix-20 Curing Agent manufactured by Struers at a ratio of 7: 1 (weight ratio)}. And left for 24 hours in an environment of 23 ° C. and 65% RH. After leaving the cured plate-shaped epoxy resin to stand at −30 ° C. for 1 hour, cross-section with a glass knife inside the ultramicrotome (made by Leica, model name: EMUC6) for measurement A sample was prepared. Next, the outer diameter of the shell (α), the diameter of the core (β), and the diameter of the largest hole (γ) that leads to the core are measured by using the SEM for the prepared sample. The average value of each 10 particles was calculated (unit [μm]).
[Characteristic evaluation]
The acrylic hollow particles and nylon particles were characterized by the method described below.
（１）圧縮率（単位［％］）：上記の方法で調製したアクリル中空粒子およびナイロン粒子を、微小圧縮試験機（島津製作所社製、型式：ＭＣＴ−Ｗ２００、以下同じ）を使用して、アクリル中空粒子およびナイロン粒子に１ｇｆの荷重をかけたときの、アクリル中空粒子およびナイロン粒子の変位量を測定した。この測定を任意に採取した１０個で行い、その平均値を算出し、次式により圧縮率を算出した。
圧縮率＝変位量の平均値／シェルの外径（α）×１００
（２）低荷重変位（単位［μｍ］）：上記の方法で調製したアクリル中空粒子、およびナイロン粒子のうち任意に採取した１０個を、微小圧縮試験機を使用して、アクリル中空粒子およびナイロン粒子に０．２ｇｆの荷重をかけたときの、アクリル中空粒子およびナイロン粒子の変位量を測定し、その平均値を算出した。(1) Compression rate (unit [%]): The acrylic hollow particles and nylon particles prepared by the above method were used using a micro compression tester (manufactured by Shimadzu Corporation, model: MCT-W200, the same shall apply hereinafter) The displacement of the acrylic hollow particles and the nylon particles when a load of 1 gf was applied to the acrylic hollow particles and the nylon particles was measured. This measurement was performed with 10 samples collected arbitrarily, the average value was calculated, and the compression rate was calculated by the following equation.
Compression rate = average value of displacement / outer diameter of shell (α) × 100
(2) Low load displacement (unit: [μm]): Acrylic hollow particles and nylon were collected by arbitrarily using 10 samples of acrylic hollow particles and nylon particles prepared by the above method. The displacement of acrylic hollow particles and nylon particles when a load of 0.2 gf was applied to the particles was measured, and the average value was calculated.
（３）官能試験（ソフト感・しっとり感・伸展性）：下記の方法で製造したアクリル粒子およびナイロン粒子について、ソフト感・しっとり感・伸展性を１０名のパネラーによる官能試験により、非常に良好：５点、良好：４点、普通：３点、やや悪い：２点、かなり悪い：１点の基準で採点し、１０名の採点を加算し、次の基準で評価した。
（基準）Ａ：４０点以上、Ｂ：３１点〜３９点、Ｃ：３０点未満
(3) Sensory test (soft feeling, moist feeling, extensibility): About acrylic particles and nylon particles produced by the following method, the soft feeling, moist feeling, extensibility are very good by the sensory test by 10 panelists. : 5 points, good: 4 points, normal: 3 points, somewhat bad: 2 points, quite bad: scored on the basis of 1 point, scored by 10 people, and evaluated according to the following criteria.
(Standard) A: 40 points or more, B: 31 points to 39 points, C: less than 30 points
表１および表２から、次のことが明らかとなる。 From Table 1 and Table 2, the following becomes clear.
１．請求項１の要件を全て満たすアクリル中空粒子は、ソフト感・しっとり感・伸展性のいずれにもバランスよく優れており、ナイロン粒子と遜色がない（実施例１〜実施例６参照）。 1. The acrylic hollow particles satisfying all the requirements of claim 1 are excellent in balance in soft feeling, moist feeling, and extensibility, and are not inferior to nylon particles (see Examples 1 to 6).
２．これに対し、（Ａ−１）成分が多いアクリル中空粒子は、伸展性が悪く、実施例１〜実施例６のアクリル中空粒子より性能が劣っている（比較例１参照）。 2. On the other hand, acrylic hollow particles with a large amount of component (A-1) have poor extensibility and are inferior in performance to acrylic hollow particles of Examples 1 to 6 (see Comparative Example 1).
３．（Ａ−１）成分が少ないアクリル中空粒子は、ソフト感・しっとり感が悪く、実施例１〜実施例６のアクリル中空粒子より性能が劣っている（比較例２参照）。 3. (A-1) The acrylic hollow particle with few components has a soft feeling and a moist feeling, and its performance is inferior to the acrylic hollow particle of Examples 1 to 6 (see Comparative Example 2).
４．コアが中空でないアクリル中実粒子やコアに通じる孔がないアクリル多孔質粒子は、実施例１〜実施例６のアクリル中空粒子ほどのソフト感・伸展性が得られず、とりわけしっとり感に劣る（比較例３、比較例４参照）。
［化粧料の調製］
＜実施例７＞
実施例１で得られたアクリル中空粒子を５重量部、ラウリン酸亜鉛を５重量部、顔料級酸化チタンを６重量部、セリサイトを３５重量部、タルクを３５．６重量部、ベンガラを０．７重量部、黄酸化鉄を２．１重量部、黒酸化鉄を０．６重量部をオスターブレンダー（大阪ケミカル社製、型式：ＳＴ−１）にて、１５７００ｒｐｍ、３分間の条件で混合した後、予め混合したトリエチルヘキサノイン５重量部とジメチコン５重量部とからなる混合液を加え、１０３００ｒｐｍ、３分間の条件で混合して化粧料を得た。
＜比較例６＞
実施例１で得られたアクリル中空粒子に代えて比較例３で得られたアクリル中空粒子を用いて、実施例７と同様の方法により化粧料を得た。
＜比較例７＞
実施例１で得られたアクリル中空粒子に代えて比較例４で得られたアクリル中空粒子を用いて、実施例７と同様の方法により化粧料を得た。
＜参考例１＞
実施例１で得られたアクリル中空粒子に代えて比較例５と同じ市販のナイロン粒子を用いて、実施例７と同様の方法により化粧料を得た。4). Acrylic solid particles whose core is not hollow and acrylic porous particles which do not have pores leading to the core do not have the soft feeling and extensibility as the acrylic hollow particles of Examples 1 to 6, and are particularly inferior in moist feeling ( (See Comparative Examples 3 and 4).
[Preparation of cosmetics]
<Example 7>
5 parts by weight of the acrylic hollow particles obtained in Example 1, 5 parts by weight of zinc laurate, 6 parts by weight of pigment grade titanium oxide, 35 parts by weight of sericite, 35.6 parts by weight of talc, 0 parts of bengara 7 parts by weight, 2.1 parts by weight of yellow iron oxide, and 0.6 parts by weight of black iron oxide were mixed in an oster blender (Osaka Chemical Co., Ltd., model: ST-1) at 15700 rpm for 3 minutes. Then, a premixed mixture of 5 parts by weight of triethylhexanoin and 5 parts by weight of dimethicone was added and mixed at 10300 rpm for 3 minutes to obtain a cosmetic.
<Comparative Example 6>
A cosmetic was obtained in the same manner as in Example 7, except that the acrylic hollow particles obtained in Comparative Example 3 were used instead of the acrylic hollow particles obtained in Example 1.
<Comparative Example 7>
A cosmetic was obtained in the same manner as in Example 7, except that the acrylic hollow particles obtained in Comparative Example 4 were used instead of the acrylic hollow particles obtained in Example 1.
<Reference Example 1>
A cosmetic was obtained in the same manner as in Example 7 using the same commercially available nylon particles as in Comparative Example 5 instead of the acrylic hollow particles obtained in Example 1.
実施例７、比較例６、比較例７および参考例１で得られた化粧料について前記の官能試験を行い、その結果を表３に示す。 The above-mentioned sensory test was performed on the cosmetics obtained in Example 7, Comparative Example 6, Comparative Example 7 and Reference Example 1, and the results are shown in Table 3.
表３から次のことが明らかとなる。 From Table 3, the following becomes clear.
１．請求項１の要件を全て満たすアクリル中空粒子を用いた化粧料は、ソフト感・しっとり感・伸展性のいずれにおいても、ナイロン粒子を用いた化粧料と遜色がない（実施例７、参考例１参照）。 1. Cosmetics using acrylic hollow particles that satisfy all of the requirements of claim 1 are inferior to cosmetics using nylon particles in any of soft feeling, moist feeling, and extensibility (Example 7, Reference Example 1). reference).
２．これに対し、コアが中空でないアクリル中実粒子やコアに通じる孔がないアクリル多孔質粒子を用いた化粧料は、実施例７の化粧料に比べソフト感・しっとり感が劣っている（比較例６、比較例７参照）。 2. On the other hand, cosmetics using acrylic solid particles whose core is not hollow or acrylic porous particles which do not have pores leading to the core are inferior in soft feeling and moist feeling compared to the cosmetic of Example 7 (Comparative Example). 6, see Comparative Example 7).
本発明に係るアクリル中空粒子は、ソフト感・しっとり感・伸展性のいずれにも優れているため、ナイロン粒子の代替品としてファンデーションやフェイスパウダーなどの化粧料に配合する粒子成分として好適に使用できる。 The acrylic hollow particles according to the present invention are excellent in both soft feeling, moist feeling, and extensibility, and can be suitably used as a particle component to be blended in cosmetics such as foundations and face powders as substitutes for nylon particles. .
Claims (10)
前記ホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）が４５〜９０重量％、前記不飽和二重結合を２個以上有するモノマー（Ａ−２）が１０〜５５重量％の割合で共重合され、
前記アクリル中空粒子は、中空であるコアと外殻であるシェルとを備え、
前記アクリル中空粒子のシェルの外径（α）は３〜１０μｍであり、
シェルの外径（α）とコアの径（β）との比｛（α）／（β）｝が、１．１〜３．５であり、
前記シェルには、前記コアに通じる孔が２以上形成され、
前記２以上の孔のうち最大の孔の径（γ）が、０．３〜２．５μｍであり、
前記コアの径（β）と前記最大の孔の径（γ）との比｛（β）／（γ）｝が、１．１〜２５．０であることを特徴とするアクリル中空粒子。A copolymer of a non-crosslinkable (meth) acrylate monomer (A-1) having a glass transition temperature of 50 ° C. or less and a monomer (A-2) having two or more unsaturated double bonds, And acrylic hollow particles comprising (meth) acrylic polymer (B),
Non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or lower of the homopolymer is 45 to 90% by weight, and a monomer having two or more unsaturated double bonds (A-2) ) Is copolymerized in a proportion of 10 to 55% by weight,
The acrylic hollow particle comprises a hollow core and a shell that is an outer shell,
The outer diameter (α) of the shell of the acrylic hollow particles is 3 to 10 μm,
The ratio {(α) / (β)} of the shell outer diameter (α) to the core diameter (β) is 1.1 to 3.5,
In the shell, two or more holes leading to the core are formed,
Of the two or more holes, the largest hole diameter (γ) is 0.3 to 2.5 μm,
Acrylic hollow particles, wherein the ratio {(β) / (γ)} of the core diameter (β) to the maximum pore diameter (γ) is 1.1 to 25.0.
ついで、得られた水性分散液に、別途に調製した（メタ）アクリル系ポリマー（Ｂ）を水性媒体に分散させた分散液を混合、撹拌し、前記水性分散液に含有するホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）、および不飽和二重結合を２個以上有するモノマー（Ａ−２）を前記（メタ）アクリル系ポリマー（Ｂ）に吸収させ、
ついで、得られた（メタ）アクリル系ポリマーを含有する水性分散液を加熱して、前記ホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）と、前記不飽和二重結合を２個以上有するモノマー（Ａ−２）とを共重合させて得る、アクリル中空粒子の製造方法であって、
前記ホモポリマーのガラス転移温度が５０℃以下の非架橋性（メタ）アクリル酸エステルモノマー（Ａ−１）が４５〜９０重量％、前記不飽和二重結合を２個以上有するモノマー（Ａ−２）が１０〜５５重量％の割合で共重合され、
得られるアクリル中空粒子は、中空であるコアと外殻であるシェルとを備え、
得られるアクリル中空粒子のシェルの外径（α）は、３〜１０μｍであり、
シェルの外径（α）とコアの径（β）との比｛（α）／（β）｝が、１．１〜３．５であり、
前記シェルには、前記コアに通じる孔が２以上形成され、
前記２以上の孔のうち最大の孔の径（γ）が、０．３〜２．５μｍであり、
前記コアの径（β）と前記最大の孔の径（γ）との比｛（β）／（γ）｝が、１．１〜２５．０であることを特徴とする、アクリル中空粒子の製造方法。Non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or lower, monomer (A-2) having two or more unsaturated double bonds, polymerization initiator (C) And an aqueous medium (D) are mixed and stirred to prepare an aqueous dispersion,
Next, the obtained aqueous dispersion was mixed with a dispersion prepared by dispersing a separately prepared (meth) acrylic polymer (B) in an aqueous medium, stirred, and glass transition of the homopolymer contained in the aqueous dispersion. The (meth) acrylic polymer (B) comprising a non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a temperature of 50 ° C. or lower and a monomer (A-2) having two or more unsaturated double bonds. To absorb,
Subsequently, the obtained aqueous dispersion containing the (meth) acrylic polymer is heated to form a non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or less. A method for producing acrylic hollow particles obtained by copolymerizing the monomer (A-2) having two or more unsaturated double bonds,
Non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or lower of the homopolymer is 45 to 90% by weight, and a monomer having two or more unsaturated double bonds (A-2) ) Is copolymerized in a proportion of 10 to 55% by weight,
The resulting acrylic hollow particles comprise a hollow core and a shell that is an outer shell,
The outer diameter (α) of the shell of the resulting acrylic hollow particles is 3 to 10 μm,
The ratio {(α) / (β)} of the shell outer diameter (α) to the core diameter (β) is 1.1 to 3.5,
In the shell, two or more holes leading to the core are formed,
Of the two or more holes, the largest hole diameter (γ) is 0.3 to 2.5 μm,
A ratio of the core diameter (β) to the maximum pore diameter (γ) {(β) / (γ)} is 1.1 to 25.0. Production method.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007091919 | 2007-03-30 | ||
| JP2007091919 | 2007-03-30 | ||
| PCT/JP2008/053983 WO2008126521A1 (en) | 2007-03-30 | 2008-03-05 | Acrylic hollow particles, process for production of the particles, and cosmetics containing the particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPWO2008126521A1 true JPWO2008126521A1 (en) | 2010-07-22 |
Family
ID=39863679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009508975A Pending JPWO2008126521A1 (en) | 2007-03-30 | 2008-03-05 | Acrylic hollow particles, method for producing acrylic hollow particles, and cosmetics containing these particles |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2008126521A1 (en) |
| KR (1) | KR20100015442A (en) |
| CN (1) | CN101652395A (en) |
| WO (1) | WO2008126521A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2419463B1 (en) | 2009-04-14 | 2022-07-20 | Dow Global Technologies LLC | Organic polymeric particles, paper coating compositions, and methods |
| JP5439102B2 (en) * | 2009-09-25 | 2014-03-12 | 積水化成品工業株式会社 | Hollow particles, production method and use thereof |
| CN104869975B (en) * | 2012-12-18 | 2018-09-07 | 日本合成化学工业株式会社 | Hair mousse acrylic resin lotion and the hair mousse containing it and method of haircuting |
| JP6460884B2 (en) * | 2015-03-31 | 2019-01-30 | 積水化成品工業株式会社 | Method for producing hollow resin particles |
| CN104892833B (en) * | 2015-05-21 | 2017-03-29 | 安徽大学 | A kind of preparation method of the hollow microgel of polyacrylic acid |
| JP2017165890A (en) * | 2016-03-17 | 2017-09-21 | 綜研化学株式会社 | Hollow particle and method for producing the same |
| US10730334B1 (en) | 2017-04-21 | 2020-08-04 | Omnova Solutions Inc. | Thermosensitive recording material |
| CN109851698B (en) * | 2018-03-22 | 2021-05-07 | 天津城建大学 | ABA type colloidal particle with multiple properties on surface and preparation method thereof |
| US20230365727A1 (en) * | 2020-09-30 | 2023-11-16 | Zeon Corporation | Hollow particles |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0735448B2 (en) * | 1988-09-30 | 1995-04-19 | 日本合成ゴム株式会社 | Crosslinked hollow polymer particles |
| KR940007353B1 (en) * | 1991-12-13 | 1994-08-16 | 고려화학 주식회사 | Process for producing a coreshell emulsion polymer and its containing dispersion |
| JP3539008B2 (en) * | 1995-10-25 | 2004-06-14 | 綜研化学株式会社 | Method for producing resin particles |
| JP3557844B2 (en) * | 1997-03-31 | 2004-08-25 | 日本ゼオン株式会社 | Amphoteric hollow polymer particles, method for producing the same, and paper coating composition using the particles |
| JP2003327632A (en) * | 2002-05-09 | 2003-11-19 | Pola Chem Ind Inc | Core/shell type polymer emulsion, powder coated with core/shell type polymer and cosmetic containing the powder |
-
2008
- 2008-03-05 WO PCT/JP2008/053983 patent/WO2008126521A1/en active Application Filing
- 2008-03-05 JP JP2009508975A patent/JPWO2008126521A1/en active Pending
- 2008-03-05 CN CN200880010836A patent/CN101652395A/en active Pending
- 2008-03-05 KR KR1020097021063A patent/KR20100015442A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100015442A (en) | 2010-02-12 |
| WO2008126521A1 (en) | 2008-10-23 |
| CN101652395A (en) | 2010-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPWO2008126521A1 (en) | Acrylic hollow particles, method for producing acrylic hollow particles, and cosmetics containing these particles | |
| JP5439102B2 (en) | Hollow particles, production method and use thereof | |
| US9217051B2 (en) | Resin particles, method for producing the resin particles, and use thereof | |
| KR101674906B1 (en) | Resin particle having convex portions on surface, method for producing same, and coating composition, coating material, and preparation for external use, each using same | |
| US9688832B2 (en) | Method for preparing macroporous polymethyl methacrylate | |
| JPWO2013161098A1 (en) | POLYMER PARTICLE, PROCESS FOR PRODUCING THE SAME, AND USE THEREOF | |
| JP6140059B2 (en) | Resin particles | |
| JP2024050739A (en) | Hollow particle and production method of the same | |
| JP5297845B2 (en) | Resin particles and their use | |
| JP5530586B2 (en) | Resin particles and their use | |
| JPH03133916A (en) | Water-based manicure | |
| EP1041095B1 (en) | Synthetic organic particles and process for the production of the same | |
| KR101924410B1 (en) | Chemically anisotropic particles and cosmetic composition comprising the same | |
| JP3465031B2 (en) | Coated pigments and cosmetics | |
| JP2003081738A (en) | Skin cosmetic including spherical porous crosslinked polymer particle | |
| JP2004027008A (en) | Resin particle and its preparation process | |
| JP4247022B2 (en) | Resin particles and cosmetics | |
| JP2016068037A (en) | Hollow resin particle and production process therefor | |
| JPH05310531A (en) | Cosmetic | |
| JP4107627B2 (en) | Make-up or solid-liquid multilayer cosmetic | |
| JP7372085B2 (en) | Pigment-containing hollow particles and method for producing the same | |
| JPH07291834A (en) | Coated pigment and cosmetic | |
| WO2016108579A1 (en) | Chemically anisotropic powder, and cosmetic composition containing same | |
| KR101683995B1 (en) | The cosmetic composition comprising the porous soft bead | |
| JP2007302566A (en) | Sebum adsorbent and skin preparation for external use blended with the same |