JP2012193244A - Resin particle for light diffusing agent, method for production thereof, and light diffusing film including the resin particle - Google Patents
Resin particle for light diffusing agent, method for production thereof, and light diffusing film including the resin particle Download PDFInfo
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- JP2012193244A JP2012193244A JP2011056919A JP2011056919A JP2012193244A JP 2012193244 A JP2012193244 A JP 2012193244A JP 2011056919 A JP2011056919 A JP 2011056919A JP 2011056919 A JP2011056919 A JP 2011056919A JP 2012193244 A JP2012193244 A JP 2012193244A
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- Prior art keywords
- particles
- light diffusing
- monomers
- resin
- diffusing agent
- 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.)
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- 239000002245 particle Substances 0.000 title claims abstract description 185
- 239000011347 resin Substances 0.000 title claims abstract description 65
- 229920005989 resin Polymers 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 108
- 239000000839 emulsion Substances 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 27
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 14
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 33
- 238000009792 diffusion process Methods 0.000 claims description 21
- 239000003505 polymerization initiator Substances 0.000 claims description 13
- 239000002344 surface layer Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 31
- 239000010408 film Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005191 phase separation Methods 0.000 description 15
- 239000004094 surface-active agent Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000003381 stabilizer Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 239000007771 core particle Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- QJRVOJKLQNSNDB-UHFFFAOYSA-N 4-dodecan-3-ylbenzenesulfonic acid Chemical compound CCCCCCCCCC(CC)C1=CC=C(S(O)(=O)=O)C=C1 QJRVOJKLQNSNDB-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- -1 for example Polymers 0.000 description 4
- 239000006224 matting agent Substances 0.000 description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- HQPMKSGTIOYHJT-UHFFFAOYSA-N ethane-1,2-diol;propane-1,2-diol Chemical compound OCCO.CC(O)CO HQPMKSGTIOYHJT-UHFFFAOYSA-N 0.000 description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical group CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical group FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920005822 acrylic binder Polymers 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- LDVVMCZRFWMZSG-OLQVQODUSA-N (3ar,7as)-2-(trichloromethylsulfanyl)-3a,4,7,7a-tetrahydroisoindole-1,3-dione Chemical class C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)Cl)C(=O)[C@H]21 LDVVMCZRFWMZSG-OLQVQODUSA-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
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-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
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NHGNTGPZNYKHHY-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCOCCOCCO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCOCCOCCO NHGNTGPZNYKHHY-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
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- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JAOCMLCXRGGNCU-UHFFFAOYSA-N bis(ethenyl) sulfite Chemical compound C=COS(=O)OC=C JAOCMLCXRGGNCU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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- 238000009775 high-speed stirring Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
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- 239000001923 methylcellulose Substances 0.000 description 1
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- ZARXZEARBRXKMO-UHFFFAOYSA-N n,n-bis(ethenyl)aniline Chemical compound C=CN(C=C)C1=CC=CC=C1 ZARXZEARBRXKMO-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
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- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
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- 235000013824 polyphenols Nutrition 0.000 description 1
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- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
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- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
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- 230000002087 whitening effect Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Optical Elements Other Than Lenses (AREA)
Abstract
【課題】光拡散性能に優れた光拡散剤用樹脂粒子、その製造方法およびそれを含む光拡散フィルムを提供することを課題とする。
【解決手段】重量平均分子量Ｍｗ２万〜８万の非架橋アクリル系樹脂種粒子が分散した水性エマルジョン中に、多官能ビニルモノマー、特定の界面活性能を有するアクリレートモノマーおよび単官能アルキル（メタ）アクリレートモノマー（但し、前記界面活性能を有するアクリレートモノマーを除く）の３種のモノマーを添加して、前記非架橋アクリル系樹脂種粒子に前記３種のモノマーを吸収および重合させることを特徴とする光拡散剤用粒子の製造方法により、上記課題を解決する。
【選択図】図１An object of the present invention is to provide a resin particle for a light diffusing agent excellent in light diffusing performance, a method for producing the same, and a light diffusing film including the same.
SOLUTION: A polyfunctional vinyl monomer, an acrylate monomer having a specific surface activity and a monofunctional alkyl (meth) acrylate are dispersed in an aqueous emulsion in which seed particles of non-crosslinked acrylic resin having a weight average molecular weight Mw of 20,000 to 80,000 are dispersed. A light comprising adding three kinds of monomers (excluding the acrylate monomer having surface-active ability) to absorb and polymerize the three kinds of monomers in the non-crosslinked acrylic resin seed particles The above problems are solved by a method for producing particles for a diffusing agent.
[Selection] Figure 1
Description
本発明は、光拡散性能に優れた光拡散剤用樹脂粒子、その製造方法およびそれを含む光拡散フィルムに関する。 The present invention relates to a resin particle for a light diffusing agent excellent in light diffusing performance, a method for producing the same, and a light diffusing film including the same.
粒径が１〜１００μｍの範囲にあり、その大きさの揃った樹脂粒子は、スペーサー、滑り性付与剤、複写機用のトナー、塗料の艶消し剤、機能性担体などに使用され、近年では、液晶分野において光拡散フィルム、防眩フィルムなどの原料としても使用されている。
例えば、光拡散フィルムは、樹脂粒子をバインダーおよび溶媒に混合した混合物を、フィルムに塗布することで製造され、フィルム表面に存在する粒子の異形性により光拡散性が発現するものと考えられている。
Resin particles having a particle size in the range of 1 to 100 μm are used for spacers, slipperiness imparting agents, toner for copying machines, matting agents for coating materials, functional carriers, etc. In the liquid crystal field, it is also used as a raw material for light diffusing films and antiglare films.
For example, a light diffusing film is manufactured by applying a mixture of resin particles in a binder and a solvent to the film, and is considered to exhibit light diffusibility due to the irregular shape of the particles present on the film surface. .
このような光拡散性を発現させるために、様々な樹脂粒子が提案されている。
例えば、特許第４０６７６９４号公報（特許文献１）には、ゴム状ポリマーを形成する重合性モノマーの懸濁重合によりゴム状ポリマーを形成する一段目反応と、次いでガラス状ポリマーを形成する重合性モノマーを添加して懸濁重合によりガラス状ポリマーを形成する二段目反応により製造される多相構造粒子を含有する軟質フィルム用艶消し剤およびこれらを含む艶消し軟質フィルムが記載されている。
この軟質フィルム用艶消し剤では、ゴム状ポリマー粒子の問題点、すなわち懸濁重合での合成段階や脱水時または乾燥時における粒子同士の凝集、融着および合一を、硬質ポリマーで表面を覆うことによって解決しようとしている。
In order to develop such light diffusibility, various resin particles have been proposed.
For example, Japanese Patent No. 4067694 (Patent Document 1) discloses a first-stage reaction that forms a rubber-like polymer by suspension polymerization of a polymerizable monomer that forms a rubber-like polymer, and then a polymerizable monomer that forms a glass-like polymer. A matting agent for a soft film containing multiphase structured particles produced by a second-stage reaction in which a glassy polymer is formed by suspension polymerization and a matte soft film containing these is described.
In this matting agent for soft film, the problem of rubber-like polymer particles, that is, the aggregation, fusion and coalescence of particles at the synthesis stage in suspension polymerization or at the time of dehydration or drying is covered with a hard polymer. Trying to solve by.
特許文献１の樹脂粒子は内部に多相構造を有するものの、２つのポリマーが共存するのみでは内部拡散性に限界があり、また一段目反応および二段目反応により得られる粒子は共に、０．１〜２０重量％の分子内にビニル基を有する多官能モノマーを使用しているので、それらの耐溶剤性が懸念され、フィルムコーティングの調製時に粘度が増加するおそれがある。
また、上記の樹脂粒子を含む従来の樹脂粒子では光拡散性が不十分であり、さらに光拡散性に優れた樹脂粒子、特に特殊な構造の樹脂粒子が望まれる。
Although the resin particles of Patent Document 1 have a multiphase structure inside, there is a limit to the internal diffusivity only by the coexistence of two polymers, and the particles obtained by the first-stage reaction and the second-stage reaction are both 0.00. Since polyfunctional monomers having a vinyl group in the molecule of 1 to 20% by weight are used, there is a concern about their solvent resistance, and the viscosity may increase during the preparation of the film coating.
Further, conventional resin particles including the above resin particles are insufficient in light diffusibility, and resin particles excellent in light diffusibility, particularly resin particles having a special structure are desired.
そこで、本発明は、上記の課題を解決し、光拡散性能に優れた光拡散剤用樹脂粒子、その製造方法およびそれを含む光拡散フィルムを提供することを課題とする。 Then, this invention solves said subject and makes it a subject to provide the resin particle for light diffusing agents excellent in light-diffusion performance, its manufacturing method, and a light-diffusion film containing the same.
本発明の発明者は、特定の重量平均分子量を有する非架橋アクリル系樹脂種粒子（コア粒子）が分散した水性エマルジョン中に、特定の３種のモノマーを添加して、種粒子に３種のモノマーを吸収させつつ重合させることにより、粒子内部が種粒子に由来するポリマーと３種のモノマー由来のポリマーとが微細に相分離した構造（ミクロ相分離構造）を有する、光拡散性能に優れた光拡散剤用粒子が得られることを見出し、本発明を完成するに到った。 The inventor of the present invention adds three specific monomers to an aqueous emulsion in which non-crosslinked acrylic resin seed particles (core particles) having a specific weight average molecular weight are dispersed, and three types of seed particles are added. By polymerizing while absorbing the monomer, the inside of the particle has a structure (micro phase separation structure) in which a polymer derived from seed particles and a polymer derived from three kinds of monomers are finely phase-separated, and has excellent light diffusion performance The inventors have found that particles for a light diffusing agent can be obtained, and have completed the present invention.
かくして、本発明によれば、重量平均分子量Ｍｗ２万〜８万の非架橋アクリル系樹脂種粒子が分散した水性エマルジョン中に、多官能ビニルモノマー、次式： Thus, according to the present invention, in the aqueous emulsion in which non-crosslinked acrylic resin seed particles having a weight average molecular weight Mw of 20,000 to 80,000 are dispersed, a polyfunctional vinyl monomer,
（式中、Ｒ１はＨまたはＣＨ2、ｍは１〜５０、ｎは１〜５０を意味する）
で表される界面活性能を有するアクリレートモノマーおよび単官能アルキル（メタ）アクリレートモノマー（但し、前記式の界面活性能を有するアクリレートモノマーを除く）の３種のモノマーを添加して、前記非架橋アクリル系樹脂種粒子に前記３種のモノマーを吸収および重合させて、前記非架橋アクリル系樹脂種粒子に由来するポリマーと前記３種のモノマー由来のポリマーとが粒子内部でミクロ相分離構造を有する光拡散剤用粒子を得ることを特徴とする光拡散剤用粒子の製造方法が提供される。
(Wherein, R1 is H or CH 2, m is 1-50, n denotes 1 to 50)
The non-crosslinked acrylic is added by adding three types of monomers, an acrylate monomer having a surface active ability and a monofunctional alkyl (meth) acrylate monomer (excluding an acrylate monomer having a surface active ability of the above formula). The resin having the three types of monomers absorbed and polymerized in the resin-based resin particles so that the polymer derived from the non-crosslinked acrylic resin seed particles and the polymer derived from the three monomers have a microphase separation structure inside the particles. There is provided a method for producing particles for a light diffusing agent, characterized by obtaining particles for a diffusing agent.
また、本発明によれば、上記の光拡散剤用粒子の製造方法により得られた光拡散剤用粒子が提供される。
さらに、本発明によれば、上記の光拡散剤用粒子１０〜５００重量部とバインダー樹脂１００重量部とを含む表面層用樹脂組成物から形成された表面層を備えることを特徴とする光拡散フィルムが提供される。
Moreover, according to this invention, the particle | grains for light diffusing agents obtained by the manufacturing method of said particle | grains for light diffusing agents are provided.
Furthermore, according to the present invention, the light diffusion device further comprises a surface layer formed from a resin composition for a surface layer containing 10 to 500 parts by weight of the light diffusing agent particles and 100 parts by weight of a binder resin. A film is provided.
本発明によれば、光拡散性能に優れた光拡散剤用樹脂粒子、その製造方法およびそれを含む光拡散フィルムを提供することができる。
すなわち、本発明の光拡散剤用樹脂粒子の製造方法では、特定の種粒子に特定の３種のモノマーを吸収させつつ重合させるので、得られた光拡散剤用樹脂粒子は、その内部に種粒子に由来するポリマーと３種のモノマー由来のポリマーとが共存して特殊な内部構造（微細な相分離構造＝ミクロ相分離構造）を形成している。さらに光拡散剤用樹脂粒子は、その表面に凹凸を有している。このように本発明の光拡散剤用樹脂粒子は、光拡散剤用樹脂粒子としての形状、その他の条件を備えつつ、光屈折率の異なる材質が混在する状態にあるために、従来の樹脂粒子では得られなかった、優れた光拡散性を発現するものと考えられる。
ADVANTAGE OF THE INVENTION According to this invention, the resin particle for light diffusing agents excellent in light-diffusion performance, its manufacturing method, and a light-diffusion film containing it can be provided.
That is, in the method for producing resin particles for light diffusing agent of the present invention, the specific seed particles are polymerized while absorbing the specific three types of monomers, and thus the obtained light diffusing agent resin particles are seeded inside. The polymer derived from the particles and the polymer derived from the three monomers coexist to form a special internal structure (fine phase separation structure = micro phase separation structure). Furthermore, the resin particles for light diffusing agents have irregularities on the surface. Thus, since the resin particles for light diffusing agent of the present invention have a shape as the resin particles for light diffusing agent and other conditions, and are in a state where materials having different light refractive indexes are mixed, conventional resin particles Thus, it is considered that excellent light diffusivity that was not obtained can be expressed.
また、本発明によれば、水性エマルジョンが重合開始剤をさらに含み、重合開始剤の半減期温度Ｔ℃から（Ｔ＋３０）℃までの温度範囲の水性エマルジョン中に３種のモノマーを添加し、続いてその温度以上で、非架橋アクリル系樹脂種粒子に３種のモノマーを吸収および重合させることにより、非架橋アクリル系樹脂種粒子と３種のモノマーとの重量比が１：０．４〜１．０であることにより、単官能アルキル（メタ）アクリレートモノマーと多官能ビニルモノマーと界面活性能を有するアクリレートモノマーとの重量比が、１：０．０３〜１．５：０．００１〜０．３であることにより、３種のモノマーが、架橋アクリル系樹脂種粒子１００ｇに対して３〜５０ｇ／分の範囲で水性エマルジョン中に添加されることにより、本発明のさらに優れた光拡散剤用樹脂粒子を得ることができる。 Moreover, according to the present invention, the aqueous emulsion further comprises a polymerization initiator, and three types of monomers are added to the aqueous emulsion in the temperature range from the half-life temperature T ° C. to (T + 30) ° C. of the polymerization initiator, The weight ratio of the non-crosslinked acrylic resin seed particles to the three monomers is 1: 0.4 to 1 by allowing the non-crosslinked acrylic resin seed particles to absorb and polymerize the non-crosslinked acrylic resin seed particles above the temperature. 0.0, the weight ratio of the monofunctional alkyl (meth) acrylate monomer, the polyfunctional vinyl monomer, and the acrylate monomer having surface activity is 1: 0.03 to 1.5: 0.001 to 0.00. 3, the three types of monomers are added to the aqueous emulsion in the range of 3 to 50 g / min with respect to 100 g of the crosslinked acrylic resin seed particles. It is possible to obtain a resin particle for excellent light diffusing agent.
すなわち、本発明の光拡散剤用樹脂粒子は、特定の種粒子と特定の３種のモノマーが特定比率で使用されると、軟質フィルムの光拡散剤（艶消し剤）として使用したときに、混練時の分散がより容易になり、柔軟性、強靱性、風合いを維持しながら、折り曲げや延伸時の白化や強度の低下がなく、透明感のある艶消し性を有するフィルムを得ることができる。フィルムの軟質の風合いは、光拡散剤用樹脂粒子の芯部が軟質であることによるものと考えられる。 That is, when the resin particle for light diffusing agent of the present invention is used as a light diffusing agent (matting agent) for a soft film, when specific seed particles and specific three types of monomers are used in a specific ratio, Dispersion at the time of kneading becomes easier, and while maintaining flexibility, toughness, and texture, there is no whitening or reduction in strength at the time of bending or stretching, and a transparent and matte film can be obtained. . The soft texture of the film is thought to be due to the soft core of the resin particles for the light diffusing agent.
本発明の光拡散剤用粒子の製造方法は、重量平均分子量Ｍｗ２万〜８万の非架橋アクリル系樹脂種粒子が分散した水性エマルジョン中に、多官能ビニルモノマー、特定の界面活性能を有するアクリレートモノマーおよび単官能アルキル（メタ）アクリレートモノマー（但し、界面活性能を有するアクリレートモノマーを除く）の３種のモノマーを添加して、前記非架橋アクリル系樹脂種粒子に３種のモノマーを吸収および重合させて、非架橋アクリル系樹脂種粒子に由来するポリマーと前記３種のモノマー由来のポリマーとが粒子内部で微細な相分離構造（ミクロ相分離構造）を有する光拡散剤用粒子を得ることを特徴とする。
すなわち、本発明の光拡散剤用粒子は、種粒子（コア粒子）として特定の非架橋ポリマー粒子を含む水性エマルジョン（エマルジョン）に、特定の単量体混合物を添加し、吸収させつつ重合させることにより製造することができる。
The method for producing particles for light diffusing agent of the present invention comprises a polyfunctional vinyl monomer and an acrylate having a specific surface active ability in an aqueous emulsion in which non-crosslinked acrylic resin seed particles having a weight average molecular weight Mw of 20,000 to 80,000 are dispersed. Add three types of monomer, monomer and monofunctional alkyl (meth) acrylate monomer (excluding acrylate monomer with surface activity), and absorb and polymerize the three types of monomer in the non-crosslinked acrylic resin seed particles And obtaining a particle for a light diffusing agent in which a polymer derived from non-crosslinked acrylic resin seed particles and a polymer derived from the above three monomers have a fine phase separation structure (micro phase separation structure) inside the particles. Features.
That is, the light diffusing agent particles of the present invention are polymerized while adding and absorbing a specific monomer mixture to an aqueous emulsion (emulsion) containing specific non-crosslinked polymer particles as seed particles (core particles). Can be manufactured.
（光拡散剤用粒子）
本発明において、「ミクロ相分離構造」とは、２種類以上の高分子を含む混合体において２種以上の高分子が相分離しており、この相の大きさが１ｎｍ以上１００ｎｍ未満、概ね数ｎｍ〜数十ｎｍ程度の大きさであるような状態（微細分散）であることをいう。相の大きさが１００ｎｍ以上の大きな分散相を含む状態（粗分散）ではない。
粒子の内部構造は、例えば、株式会社日立ハイテクノロジーズ製、型式：Ｈ−７６００のような透過型電子顕微鏡（ＴＥＭ）による粒子断面の観察により確認できる。観察の前処理としては、例えば、エポキシ樹脂包埋法を用いて、四酸化ルテニウム（ＲｕＯ4）染色を行ない、超薄切片作成する方法が挙げられる。
(Particle for light diffusing agent)
In the present invention, the “micro phase separation structure” means that two or more kinds of polymers are phase-separated in a mixture containing two or more kinds of polymers, and the size of this phase is 1 nm or more and less than 100 nm, and is approximately several. It means a state (fine dispersion) having a size of about nm to several tens of nm. It is not a state (coarse dispersion) including a large dispersed phase having a phase size of 100 nm or more.
The internal structure of the particles can be confirmed, for example, by observing the cross section of the particles with a transmission electron microscope (TEM) such as model: H-7600 manufactured by Hitachi High-Technologies Corporation. As a pretreatment for observation, for example, an epoxy resin embedding method is used, and ruthenium tetroxide (RuO 4 ) staining is performed to prepare an ultrathin section.
本発明の光拡散剤用粒子は、２〜１００μｍの範囲の平均粒子径を有するのが好ましい。より好ましい平均粒子径は、４〜９０μｍの範囲である。
光拡散剤用粒子の平均粒子径が２μｍ未満では、光透過性が低下することがある。一方、１００μｍを超えると、光拡散性能が低下することがある。
The light diffusing agent particles of the present invention preferably have an average particle diameter in the range of 2 to 100 μm. A more preferable average particle diameter is in the range of 4 to 90 μm.
If the average particle diameter of the light diffusing agent particles is less than 2 μm, the light transmittance may be lowered. On the other hand, when it exceeds 100 μm, the light diffusion performance may be deteriorated.
以下に、本発明の光拡散剤用粒子の製造方法について、種粒子の製造（第一工程）、３種のモノマーの混合物（水性エマルジョン）の調製（第二工程）および３種のモノマーの吸収および重合（第三工程）に分けてより具体的に説明するが、これにより本発明が限定されるものではない。 Below, regarding the method for producing the light diffusing agent particles of the present invention, production of seed particles (first step), preparation of a mixture of three types of monomers (aqueous emulsion) (second step), and absorption of the three types of monomers However, the present invention is not limited to this, although it will be described in more detail by dividing it into polymerization (third step).
（１）第一工程
ここで製造する種粒子は、コア粒子ともいい、重量平均分子量Ｍｗ２万〜８万の非架橋アクリル系樹脂からなる。好ましい種粒子の重量平均分子量Ｍｗは、３万〜７万の範囲である。
重量平均分子量Ｍｗが２万未満では、種粒子を得るための重合が長時間化することがある。一方、重量平均分子量Ｍｗが８万を超えると、種粒子に３種のモノマーが吸収し難くなることがある。重量平均分子量の測定方法については、実施例で詳述する。
(1) 1st process The seed particle manufactured here is also called a core particle, and consists of non-crosslinked acrylic resin with a weight average molecular weight Mw 20,000-80,000. The weight average molecular weight Mw of the preferred seed particles is in the range of 30,000 to 70,000.
When the weight average molecular weight Mw is less than 20,000, polymerization for obtaining seed particles may take a long time. On the other hand, when the weight average molecular weight Mw exceeds 80,000, it may be difficult for the seed particles to absorb the three kinds of monomers. The method for measuring the weight average molecular weight will be described in detail in Examples.
種粒子は、１．５〜９０μｍの平均粒子径を有するのが好ましい。
平均粒子径が１．５μｍ未満では、重合時にコア粒子が凝集してしまい、内部構造が形成されないことがある。一方、９０μｍを超えると、コア粒子に特定の単量体混合物がうまく吸収されないことがある。より好ましい平均粒子径は、３〜８０μｍである。粒子の平均粒子径の測定方法については、実施例で詳述する。
The seed particles preferably have an average particle size of 1.5 to 90 μm.
If the average particle size is less than 1.5 μm, the core particles may aggregate during polymerization, and the internal structure may not be formed. On the other hand, when it exceeds 90 μm, the specific monomer mixture may not be absorbed well into the core particles. A more preferable average particle diameter is 3 to 80 μm. The method for measuring the average particle diameter of the particles will be described in detail in Examples.
非架橋アクリル系樹脂としては、特に限定されないが、本発明においては、粒子の耐溶剤性、分散性、凝集性の点で、第二工程で用いる単官能アルキル（メタ）アクリレートモノマーからなる樹脂が好ましい。
単官能アルキル（メタ）アクリレートモノマー（但し、後述する式の界面活性能を有するアクリレートモノマーを除く）としては、例えば、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸ブチル、メタクリル酸ブチル、アクリル酸イソブチル、メタクリル酸イソブチル、アクリル酸ターシャリーブチル、メタクリル酸ターシャリーブチル、アクリル酸２−エチルヘキシル、メタクリル酸２−エチルヘキシル、アクリル酸ステアリル、メタクリル酸ステアリルなどが挙げられる。これらの中でも、アクリル酸ブチル、メタクリル酸ブチル、アクリル酸イソブチル、メタクリル酸イソブチル、アクリル酸ターシャリーブチル、メタクリル酸ターシャリーブチルが特に好ましい。これらは、１種を単独で使用してもまたは２種以上を併用してもよい。また、アルキル（メタ）アクリレートモノマーの使用量を７０重量％以上として、スチレン、α―メチルスチレン、ビニルトルエン、クロロスチレンなどのビニル系モノマーと併用してもよい。
The non-crosslinked acrylic resin is not particularly limited, but in the present invention, a resin composed of a monofunctional alkyl (meth) acrylate monomer used in the second step is used in terms of solvent resistance, dispersibility, and cohesiveness of the particles. preferable.
Examples of monofunctional alkyl (meth) acrylate monomers (excluding acrylate monomers having a surface-active ability of the formula described below) include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, Examples include butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, stearyl acrylate, and stearyl methacrylate. Among these, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tertiary butyl acrylate, and tertiary butyl methacrylate are particularly preferable. These may be used alone or in combination of two or more. Further, the alkyl (meth) acrylate monomer may be used in an amount of 70% by weight or more, and may be used in combination with vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, and chlorostyrene.
種粒子は、公知の方法により製造することができるが、本発明においては、粒子径の調整の容易さなどの点で、懸濁重合法により製造されたものが特に好ましい。
具体的には、水に懸濁安定剤を加えた分散相に、界面活性剤および重合禁止剤をさらに加え、上記のアクリル系樹脂のモノマーおよび重合開始剤を加え、高速攪拌し、水性エマルジョンの状態でモノマーを重合させる。
重合温度および時間は、用いる材料や重合条件などにより適宜設定すればよく、５０〜
１００℃程度、１〜５時間程度である。
ここで「水性エマルジョン」とは、水などの水性媒体中にモノマー成分などが懸濁されたものを意味し、その濃度は、重合反応が阻害されない程度であればよく、モノマー成分などが水性媒体中に０．５〜５００ｇ／ｌ程度である。
The seed particles can be produced by a known method, but in the present invention, those produced by a suspension polymerization method are particularly preferred from the viewpoint of easy adjustment of the particle diameter.
Specifically, a surfactant and a polymerization inhibitor are further added to a dispersed phase obtained by adding a suspension stabilizer to water, the above-mentioned acrylic resin monomer and polymerization initiator are added, and the mixture is stirred at a high speed. The monomer is polymerized in the state.
The polymerization temperature and time may be appropriately set depending on the material used, polymerization conditions, etc.
It is about 100 degreeC and about 1 to 5 hours.
As used herein, the term “aqueous emulsion” means that the monomer component is suspended in an aqueous medium such as water, and the concentration thereof may be such that the polymerization reaction is not hindered. It is about 0.5 to 500 g / l.
懸濁安定剤（分散安定剤）としては、一般にポリマーの懸濁重合に用いられる分散安定剤、例えば、メチルセルロース、ヒドロキシエチルセルロース、ポリビニルアルコールなどの水溶性高分子、第三リン酸カルシウム、水酸化マグネシウム、ピロリン酸マグネシウム、硫酸バリウム、炭酸カルシウム、シリカなどの難水溶性無機塩が挙げられる。その使用量は、用いる材料や重合条件などにより適宜設定すればよく、モノマー成分１００重量部に対して１０〜６０重量部程度である。 As the suspension stabilizer (dispersion stabilizer), a dispersion stabilizer generally used for suspension polymerization of polymers, for example, water-soluble polymers such as methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, tricalcium phosphate, magnesium hydroxide, pyrroline Examples include poorly water-soluble inorganic salts such as magnesium acid, barium sulfate, calcium carbonate, and silica. The amount used may be appropriately set depending on the material used, polymerization conditions, and the like, and is about 10 to 60 parts by weight with respect to 100 parts by weight of the monomer component.
界面活性剤としては、例えば、ラウリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ソーダ、α−オレフィンスルホン酸ソーダなどが挙げられる。懸濁安定剤として無機系分散剤を用いる場合には、分散安定性および粒子径調整の点で、界面活性剤を併用することが好ましい。その使用量は、用いる材料や重合条件などにより適宜設定すればよく、モノマー成分１００重量部に対して０．１〜２０重量部程度である。 Examples of the surfactant include sodium lauryl sulfate, sodium dodecylbenzene sulfonate, and sodium α-olefin sulfonate. When an inorganic dispersant is used as the suspension stabilizer, it is preferable to use a surfactant in combination from the viewpoint of dispersion stability and particle size adjustment. The amount used may be appropriately set depending on the material used, polymerization conditions, etc., and is about 0.1 to 20 parts by weight with respect to 100 parts by weight of the monomer component.
重合禁止剤としては、例えば、亜硝酸塩類、亜硫酸塩類、ハイドロキノン類、アスコルビン酸類、水溶性ビタミンＢ類、クエン酸、ポリフェノール類等の水溶性ものが挙げられる。なお、重合禁止剤は、単独で用いられても併用されてもよい。 Examples of the polymerization inhibitor include water-soluble substances such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citric acid, and polyphenols. The polymerization inhibitor may be used alone or in combination.
重合開始剤としては、例えば、アクリル系樹脂モノマーの重合に汎用されている従来周知の重合開始剤を使用できる。例えば、過酸化ベンゾイル、過酸化ラウロイル、オルソクロロ過酸化ベンゾイル、オルソメトキシ過酸化ベンゾイル、３，５，５−トリメチルヘキサノイルパーオキサイド、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ジ−ｔ−ブチルパーオキサイドなどの有機過酸化物、アゾビスイソブチロニトリル、アゾビスシクロヘキサカルボニトリル、アゾビス（２，４−ジメチルベレロニトリル）などのアゾ系化合物が挙げられる。なお、重合開始剤は、単独で用いられても併用されてもよい。その使用量は、用いる材料や重合条件などにより適宜設定すればよく、モノマー成分１００重量部に対して０．０１〜５重量部程度である。 As a polymerization initiator, the conventionally well-known polymerization initiator currently used widely for superposition | polymerization of an acrylic resin monomer can be used, for example. For example, benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, di-t- Examples thereof include organic peroxides such as butyl peroxide, and azo compounds such as azobisisobutyronitrile, azobiscyclohexacarbonitrile, and azobis (2,4-dimethylbereronitrile). In addition, a polymerization initiator may be used independently or may be used together. The amount used may be appropriately set depending on the material used, polymerization conditions, and the like, and is about 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer component.
本発明では、非架橋アクリル系樹脂種粒子が、アルキル（メタ）アクリレートモノマー１００重量部に対してメルカプタン系連鎖移動剤０．０５〜１５重量部、好ましくは０．１〜１０重量部を添加し、懸濁重合させた重合体であるのが好ましい。これにより、本発明のさらに優れた光拡散剤用樹脂粒子を効率よく得ることができる。
メルカプタン系連鎖移動剤が０．０５重量部未満では、重量平均分子量Ｍｗが８万を超えてしまい、第一反応物の重合体へ第二のモノマー混合物が吸収され難くなることがある。一方、メルカプタン系連鎖移動剤が１５重量部を超えると、重量平均分子量Ｍｗが２万未満になる一方で、第一反応物の重合完了に長時間を要し、生産性が悪化することがある。
メルカプタン系連鎖移動剤としては、例えば、n-オクチルメルカプタン、ｎ-ドデシルメルカプタン、ｔ−ドデシルメルカプタン、２−ヒドロキシエチルメルカプタン、ラウリルメルカプタン、ステアリルメルカプタンなどのカプタン系化合物、α-メチルスチレンダイマー(ＣＨ2＝ＣＰｈＣＨ2Ｃ（ＣＨ3）2Ｐｈ[ただしＰｈはフェニル基である])のような芳香族系化合物などが挙げられる。なお、メルカプタン系連鎖移動剤は、単独で用いられても併用されてもよい。
In the present invention, the non-crosslinked acrylic resin seed particles are added in an amount of 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight of a mercaptan chain transfer agent with respect to 100 parts by weight of the alkyl (meth) acrylate monomer. A polymer obtained by suspension polymerization is preferred. Thereby, the further excellent resin particle for light diffusing agents of this invention can be obtained efficiently.
When the mercaptan chain transfer agent is less than 0.05 parts by weight, the weight average molecular weight Mw exceeds 80,000, and the second monomer mixture may be difficult to be absorbed by the polymer of the first reactant. On the other hand, when the mercaptan chain transfer agent exceeds 15 parts by weight, the weight average molecular weight Mw becomes less than 20,000, while it takes a long time to complete the polymerization of the first reactant and the productivity may deteriorate. .
Examples of mercaptan chain transfer agents include captan compounds such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 2-hydroxyethyl mercaptan, lauryl mercaptan, stearyl mercaptan, α-methylstyrene dimer (CH 2 = CPhCH 2 C (CH 3 ) 2 Ph [where Ph is a phenyl group])). The mercaptan chain transfer agent may be used alone or in combination.
（２）第二工程
ここで３種のモノマー、すなわち単官能アルキル（メタ）アクリレートモノマー、多官能ビニルモノマーおよび界面活性能を有するアクリレートモノマーの水性エマルジョンを製造する。具体的には、水に界面活性剤を加え、次いでこれらの３種のモノマーを加え、高速攪拌して水性エマルジョンを得る。この水性エマルジョンには、重合開始剤が含まれていてもよい。
ここで「水性エマルジョン」とは、水などの水性媒体中にモノマー成分などが懸濁されたものを意味し、その濃度は、重合反応が阻害されない程度であればよく、モノマー成分などが水性媒体中に０．５〜５００ｇ／ｌ程度である。
(2) Second Step Here, an aqueous emulsion of three types of monomers, that is, a monofunctional alkyl (meth) acrylate monomer, a polyfunctional vinyl monomer, and an acrylate monomer having surface active ability is produced. Specifically, a surfactant is added to water, and then these three types of monomers are added and stirred at high speed to obtain an aqueous emulsion. This aqueous emulsion may contain a polymerization initiator.
As used herein, the term “aqueous emulsion” means that the monomer component is suspended in an aqueous medium such as water, and the concentration thereof may be such that the polymerization reaction is not hindered. It is about 0.5 to 500 g / l.
単官能アルキル（メタ）アクリレートモノマー（但し、後述する式の界面活性能を有するアクリレートモノマーを除く）としては、種粒子の非架橋アクリル系樹脂を構成するモノマーで例示したアルキル（メタ）アクリレートモノマー、例えば、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸ブチル、メタクリル酸ブチル、アクリル酸イソブチル、メタクリル酸イソブチル、アクリル酸ターシャリーブチル、メタクリル酸ターシャリーブチル、アクリル酸２−エチルヘキシル、メタクリル酸２−エチルヘキシル、アクリル酸ステアリル、メタクリル酸ステアリルなどが挙げられる。これらは、１種を単独で使用してもまたは２種以上を併用してもよい。 As the monofunctional alkyl (meth) acrylate monomer (excluding the acrylate monomer having the surface active ability of the formula described later), the alkyl (meth) acrylate monomer exemplified as the monomer constituting the non-crosslinked acrylic resin of the seed particles, For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-acrylic acid 2- Examples include ethylhexyl, 2-ethylhexyl methacrylate, stearyl acrylate, stearyl methacrylate, and the like. These may be used alone or in combination of two or more.
多官能ビニルモノマーの「多官能」とは、重合性の二重結合を２個以上有する、すなわち一分子中に２つ以上のビニル基を含有することを意味する。
多官能ビニルモノマーとしては、例えば、ジビニルベンゼン、ジビニルナフタレンおよびそれらの誘導体などの芳香族ジビニル化合物、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールトリアクリレート、トリメチロールプロパントリアクリレートなどのジエチレン性カルボン酸エステル、Ｎ，Ｎ−ジビニルアニリン、ジビニルエーテル、ジビニルスルファイトなどのジビニル化合物ならびにビニル基を３個以上有する化合物などが挙げられる。これらは、１種を単独で使用してもまたは２種以上を併用してもよい。
The “polyfunctional” of the polyfunctional vinyl monomer means having two or more polymerizable double bonds, that is, containing two or more vinyl groups in one molecule.
Examples of the polyfunctional vinyl monomer include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and derivatives thereof, and diethylenic carboxylic acids such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol triacrylate, and trimethylolpropane triacrylate. Examples thereof include divinyl compounds such as acid esters, N, N-divinylaniline, divinyl ether and divinyl sulfite, and compounds having three or more vinyl groups. These may be used alone or in combination of two or more.
界面活性能を有するアクリレートモノマーは、次式： The acrylate monomer having surface active ability has the following formula:
（式中、Ｒ１はＨまたはＣＨ2、ｍは１〜５０、ｎは１〜５０を意味する）
で表される。「界面活性能を有する」とは、上記式のアクリレートモノマーが界面活性剤の機能を有することを意味する。
具体的には、ポリ（エチレングリコール−プロピレングリコール）モノメタクリレート、例えば、日油株式会社製のブレンマー５０ＰＥＰ−３００、ブレンマー７０ＰＥＰ−３５０Ｂなどのブレンマーシリーズなどが挙げられる。これらは、１種を単独で使用してもまたは２種以上を併用してもよい。
(Wherein, R1 is H or CH 2, m is 1-50, n denotes 1 to 50)
It is represented by “Having surfactant activity” means that the acrylate monomer of the above formula has a surfactant function.
Specifically, poly (ethylene glycol-propylene glycol) monomethacrylate, for example, Blemmer series such as Blemmer 50PEP-300, Blemmer 70PEP-350B manufactured by NOF Corporation, and the like can be mentioned. These may be used alone or in combination of two or more.
単官能アルキル（メタ）アクリレートモノマー［Ａ］と多官能ビニルモノマー［Ｂ］と界面活性能を有するアクリレートモノマー［Ｃ］との重量比Ａ：Ｂ：Ｃは、１：０．０３〜１．５：０．００１〜０．３であるのが好ましい。
［Ｂ］の割合が０．０３未満では、得られた樹脂粒子が溶剤に溶解してしまい、塗料添加物としての役割を果たさないことがある。一方、［Ｂ］の割合が１．５を超えると、得られた樹脂粒子の表面に凸形状が得られないこと、得られた樹脂粒子の硬度が高くなり、塗物にした場合にその他の部材に傷をつけてしまうことがある。より好ましい［Ｂ］の範囲は０．１〜１．２である。
また、［Ｃ］の割合が０．００１未満では、得られた樹脂粒子の内部が微細な相分離構造（ミクロ相分離構造）とならず、樹脂粒子表面に凸形状が得られないことがある。一方、［Ｃ］の割合が０．３を超えると、重合安定性が悪くなり、凝集体が多く発生することがある。より好ましい［Ｃ］の範囲は０．０１〜０．２である。
The weight ratio A: B: C of the monofunctional alkyl (meth) acrylate monomer [A], the polyfunctional vinyl monomer [B], and the acrylate monomer [C] having surface activity is 1: 0.03 to 1.5. : 0.001 to 0.3 is preferable.
If the ratio of [B] is less than 0.03, the obtained resin particles may be dissolved in a solvent and may not serve as a paint additive. On the other hand, if the ratio of [B] exceeds 1.5, a convex shape cannot be obtained on the surface of the obtained resin particles, the hardness of the obtained resin particles becomes high, and when the coating is used, The member may be damaged. A more preferable range of [B] is 0.1 to 1.2.
Moreover, when the ratio of [C] is less than 0.001, the inside of the obtained resin particles does not have a fine phase separation structure (micro phase separation structure), and a convex shape may not be obtained on the surface of the resin particles. . On the other hand, when the ratio of [C] exceeds 0.3, the polymerization stability is deteriorated, and a large number of aggregates may be generated. A more preferable range of [C] is 0.01 to 0.2.
界面活性剤および重合開始剤は、それぞれ第一工程で例示のものが挙げられ、それらの使用量は、用いる材料や重合条件などにより適宜設定すればよく、それぞれモノマー成分１００重量部に対して１〜２０重量部程度および０．０１〜５．０重量部程度である。 Examples of the surfactant and the polymerization initiator include those exemplified in the first step, and the amount used thereof may be appropriately set depending on the material used, the polymerization conditions, and the like, and is 1 for each 100 parts by weight of the monomer component. About 20 parts by weight and about 0.01-5.0 parts by weight.
（３）第三工程
第一工程で得られた種粒子に、３種のモノマーを吸収および重合させて、種粒子に由来するポリマーと前記３種のモノマー由来のポリマーとが粒子内部でミクロ相分離構造を有する光拡散剤用粒子を得る。具体的には、第一工程で得られた種粒子の水性エマルジョンに、第二工程で得られた３種のモノマーの水性エマルジョンを滴下して、３種のモノマーを吸収および重合させる。
ここで「水性エマルジョン」とは、水などの水性媒体中に種粒子またはモノマー成分などが懸濁されたものを意味し、その濃度は、重合反応が阻害されない程度であればよく、種粒子またはモノマー成分などが水性媒体中に０．５〜５００ｇ／ｌ程度である。
重合後、得られた樹脂粒子を、公知の方法により、後処理を経て分離回収する。
(3) Third step The seed particles obtained in the first step absorb and polymerize three types of monomers, and the polymer derived from the seed particles and the polymer derived from the three types of monomers are microphased inside the particles. A light diffusing agent particle having a separation structure is obtained. Specifically, the aqueous emulsion of the three types of monomers obtained in the second step is dropped into the aqueous emulsion of the seed particles obtained in the first step to absorb and polymerize the three types of monomers.
Here, the “aqueous emulsion” means a suspension of seed particles or monomer components in an aqueous medium such as water, and the concentration thereof may be such that the polymerization reaction is not hindered. A monomer component etc. are about 0.5-500 g / l in an aqueous medium.
After polymerization, the obtained resin particles are separated and recovered through post-treatment by a known method.
水性エマルジョンが重合開始剤をさらに含み、前記重合開始剤の半減期温度Ｔ℃から（Ｔ＋３０）℃までの温度範囲の水性エマルジョン中に３種のモノマーを添加し、続いてその温度以上で、前記非架橋アクリル系樹脂種粒子に前記３種のモノマーを吸収および重合させるのが好ましい。
例えば、重合開始剤としてアゾビスイソブチルニトリルを用いる場合、その半減期温度は６０℃であり、６０℃で種粒子の水性エマルジョンに３種のモノマーのエマルジョンを滴下し、６５℃で重合させることができる。
重合時間は、用いる材料や重合条件などにより適宜設定すればよく、２〜６時間程度である。
The aqueous emulsion further comprises a polymerization initiator, and three monomers are added to the aqueous emulsion in the temperature range from the half-life temperature T ° C. to (T + 30) ° C. of the polymerization initiator, and then above that temperature, It is preferable that non-crosslinked acrylic resin seed particles absorb and polymerize the three kinds of monomers.
For example, when azobisisobutylnitrile is used as a polymerization initiator, its half-life temperature is 60 ° C., and an emulsion of three types of monomers is dropped into an aqueous emulsion of seed particles at 60 ° C. and polymerized at 65 ° C. it can.
The polymerization time may be appropriately set depending on the material used, polymerization conditions, etc., and is about 2 to 6 hours.
３種のモノマーを、非架橋アクリル系樹脂種粒子１００ｇに対して３〜５０ｇ／分の範囲で種粒子の水性エマルジョン中に添加されるのが好ましい。
３種のモノマー添加速度が３ｇ／分未満では、吸収よりも重合が進んでしまい、粒子内部に微細な相分離構造（ミクロ相分離構造）が形成されないことがある。５〜４０ｇ／分がより好ましい。一方、３種のモノマー添加速度が５０ｇ／分を超えると、吸収される前に重合が進行してしまい、３種モノマーが単独で重合してしまうことがある。実施例では、このような添加速度からして、添加時間は５〜１５分間程度である。
The three types of monomers are preferably added to the aqueous emulsion of seed particles in the range of 3 to 50 g / min with respect to 100 g of non-crosslinked acrylic resin seed particles.
When the rate of addition of the three types of monomers is less than 3 g / min, polymerization proceeds more than absorption, and a fine phase separation structure (micro phase separation structure) may not be formed inside the particles. 5-40 g / min is more preferable. On the other hand, when the addition rate of the three types of monomers exceeds 50 g / min, the polymerization proceeds before being absorbed, and the three types of monomers may be polymerized alone. In an Example, from such an addition rate, addition time is about 5 to 15 minutes.
非架橋アクリル系樹脂種粒子と前記３種のモノマーとの重量比は、１：０．４〜１．０であるのが好ましい。
３種のモノマーの割合０．４未満では、架橋アクリル系樹脂種粒子の割合が多くなり、粒子内部が微細な相分離構造（ミクロ相分離構造）にならない場合がある。一方、３種のモノマーの割合が１．０を超えると、吸収分が多く、吸収しきれなかったモノマーが単独で重合してしまうことがある。より好ましい３種のモノマーの範囲は０．５〜１．０である。
The weight ratio between the non-crosslinked acrylic resin seed particles and the three monomers is preferably 1: 0.4 to 1.0.
If the ratio of the three kinds of monomers is less than 0.4, the ratio of the cross-linked acrylic resin seed particles increases, and the inside of the particles may not have a fine phase separation structure (microphase separation structure). On the other hand, if the ratio of the three types of monomers exceeds 1.0, the amount of absorption is large, and the monomer that could not be absorbed may be polymerized alone. A more preferable range of the three types of monomers is 0.5 to 1.0.
種粒子と３種のモノマーとの相溶性、すなわち種粒子への３種のモノマーの吸収が調整されることにより、相分離反応および体積収縮が起こり、樹脂粒子内部に微細な相分離構造（ミクロ相分離構造）が形成される。 By adjusting the compatibility of the seed particles with the three types of monomers, that is, the absorption of the three types of monomers into the seed particles, a phase separation reaction and volume shrinkage occur, and a fine phase separation structure (microscopic) is formed inside the resin particles. Phase separation structure) is formed.
（光拡散フィルム）
本発明の光拡散フィルムは、本発明の光拡散剤用粒子１０〜５００重量部とバインダー樹脂１００重量部とを含む表面層用樹脂組成物から形成された表面層を備えることを特徴とする。
バインダー樹脂は、表面層用樹脂組成物を調製し得る樹脂であれば特に限定されず、例えば、実施例で用いられているようなアクリルバインダーが挙げられる。
そして、本発明の光拡散フィルムは、例えば、本発明の光拡散剤用粒子、バインダー樹脂、溶剤などを公知の方法により混合して分散液を調製し、これを公知の方法により基材となるフィルム上に塗布・乾燥することにより得ることができる。
(Light diffusion film)
The light diffusion film of the present invention comprises a surface layer formed from a resin composition for a surface layer comprising 10 to 500 parts by weight of the light diffusing agent particles of the present invention and 100 parts by weight of a binder resin.
Binder resin will not be specifically limited if it is resin which can prepare the resin composition for surface layers, For example, the acrylic binder used in the Example is mentioned.
And the light-diffusion film of this invention mixes the particle | grains for light-diffusion agents of this invention, binder resin, a solvent, etc. by a well-known method, for example, prepares a dispersion liquid, This becomes a base material by a well-known method. It can be obtained by coating and drying on a film.
以下、製造例、比較製造例、実施例および比較例により本発明を具体的に説明するが、本発明はこれらの製造例および実施例により限定されるものではない。
まず、樹脂粒子の重量平均分子量Ｍｗ、平均粒子径および変動係数、光拡散フィルムのヘイズの測定方法について説明する。
Hereinafter, the present invention will be specifically described with reference to production examples, comparative production examples, examples, and comparative examples, but the present invention is not limited to these production examples and examples.
First, the measurement method of the weight average molecular weight Mw of a resin particle, an average particle diameter, a variation coefficient, and the haze of a light-diffusion film is demonstrated.
（重量平均分子量Ｍｗ）
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて、次のようにして重量平均分子量を測定する。なお、重量平均分子量は、ポリスチレン（ＰＳ）換算重量平均分子量を意味する。
具体的には、試料３ｍｇを１０ｍｌのテトラヒドロフラン（ＴＨＦ）に加えて、一晩放置して溶解させ、０．４５μｍのフィルターで濾過して、測定試料を得る。得られた試料を下記の装置および条件で重量平均分子量を測定する。
測定装置：ゲルパーミエーションクロマトグラフ（東ソー株式会社製、型式：ＨＬＣ−８３２０）
ガードカラム：東ソー株式会社製、製品名：TSＫguardcolumn SuperHZ-H
φ４．６ｍｍ×１５ｃｍＬ×１本
カラム ：東ソー株式会社製、製品名：ＴＳＫｇｅｌ SuperHZM−H
φ４．６ｍｍ×１５ｃｍＬ×２本
測定条件 ：カラム温度（４０℃）、移動相（試薬一級ＴＨＦ）、
移動相流量（０．１７５ｍｌ／min），注入量（５０μｌ）、
測定時間（２５min）、検出器（ＲＩ）
検量線用標準ポリスチレン：
重量平均分子量：１０３００００（昭和電工株式会社製、商品名：ｓｈｏｄｅｘ）
重量平均分子量：５４８００００、３８４００００、３５５０００、１０２０００
３７９００、９１００、２６３０、５００（東ソー株式会社製）
(Weight average molecular weight Mw)
Using gel permeation chromatography (GPC), the weight average molecular weight is measured as follows. In addition, a weight average molecular weight means a polystyrene (PS) conversion weight average molecular weight.
Specifically, 3 mg of a sample is added to 10 ml of tetrahydrofuran (THF), left to dissolve overnight, and filtered through a 0.45 μm filter to obtain a measurement sample. The weight average molecular weight of the obtained sample is measured with the following apparatus and conditions.
Measuring apparatus: Gel permeation chromatograph (manufactured by Tosoh Corporation, model: HLC-8320)
Guard column: manufactured by Tosoh Corporation, product name: TSKguardcolumn SuperHZ-H
φ4.6mm × 15cmL × 1 Column: manufactured by Tosoh Corporation, product name: TSKgel SuperHZM-H
φ4.6 mm × 15 cmL × 2 Measurement conditions: Column temperature (40 ° C.), mobile phase (reagent primary THF),
Mobile phase flow rate (0.175 ml / min), injection volume (50 μl),
Measurement time (25 min), detector (RI)
Standard polystyrene for calibration curve:
Weight average molecular weight: 1030000 (made by Showa Denko KK, trade name: shodex)
Weight average molecular weight: 5480000, 3840000, 355000, 102000
37900, 9100, 2630, 500 (manufactured by Tosoh Corporation)
（樹脂粒子の平均粒子径および変動係数）
平均粒子径及びＣＶ値は、Ｃｏｕｌｔｅｒ Ｅｌｅｃｔｒｏｎｉｃｓ Ｌｉｍｉｔｅｄ発行のＲｅｆｅｒｅｎｃｅ ＭＡＮＵＡＬ ＦＯＲＴＨＥＣＯＵＬＴＥＲＭＵＬＴＩＳＩＺ ＥＲ（１９８７）に従って、Ｘμｍサイズのアパチャーを用いてキャリブレーションを行い測定する。
具体的には、樹脂粒子０．１ｇを０．１％ノニオン系界面活性剤１０ｍｌ中にタッチミキサーおよび超音波を用いて予備分散させ、これを本体備え付けのＩＳＯＴＯＮII（ベックマンコールター社：測定用電解液）を満たしたビーカー中に、緩く撹拌しながらスポイドで滴下して、本体画面の濃度計の示度を１０％前後に合わせる。次にコールターマルチサイザーIII（ベックマンコールター社製：測定装置）本体にアパチャーサイズＸμｍをセットし、Ｃｕｒｒｅｎｔ、Ｇａｉｎ、Ｐｏｌａｒｉｔｙをアパチャーサイズに合わせた所定の条件で測定を行う。測定中はビーカー内を気泡が入らない程度に緩く撹拌しておき、粒子を１０万個測定した時点で測定を終了する。体積加重の平均径（体積％モードの算術平均径：体積メジアン径）を樹脂粒子の平均粒子径（Ｘ）として算出する。
アパチャーサイズＸμｍは、平均粒子径が１μｍ未満の樹脂粒子に対しては２０μｍであり、１〜１０μｍ未満の樹脂粒子に対しては５０μｍであり、平均粒子径が１０〜３０μｍ未満の樹脂粒子に対しては細孔径１００μｍであり、平均粒子径が３０〜９０μｍ未満を超える樹脂粒子に対しては細孔径２８０μｍであり、平均粒子径が９０μｍを超える樹脂粒子に対しては細孔径４００μｍである。
変動係数（ＣＶ値）とは、標準偏差（σ）および上記平均粒子径（Ｘ）から次式により算出された値である。
ＣＶ値（％）＝（σ／Ｘ）×１００
(Average particle diameter and coefficient of variation of resin particles)
The average particle size and the CV value are measured by calibration using an aperture of X μm size in accordance with Reference MANUAL FORTHEULTURE MULTISIZER ER (1987) published by Coulter Electronics Limited.
Specifically, 0.1 g of resin particles are preliminarily dispersed in 10 ml of 0.1% nonionic surfactant using a touch mixer and ultrasonic waves, and this is provided with ISOTON II (Beckman Coulter, Inc .: electrolyte for measurement) provided in the main body. ) In a beaker filled with), drop with a dropper while gently stirring, and adjust the reading of the densitometer on the main body screen to about 10%. Next, the aperture size X μm is set in the body of Coulter Multisizer III (manufactured by Beckman Coulter, Inc .: measuring device), and measurement is performed under predetermined conditions in which Current, Gain, and Polarity are matched to the aperture size. During the measurement, the beaker is stirred gently to the extent that bubbles do not enter, and the measurement is terminated when 100,000 particles are measured. The volume-weighted average diameter (arithmetic average diameter in volume% mode: volume median diameter) is calculated as the average particle diameter (X) of the resin particles.
The aperture size X μm is 20 μm for resin particles having an average particle diameter of less than 1 μm, 50 μm for resin particles having an average particle diameter of less than 1 to 10 μm, and for resin particles having an average particle diameter of less than 10 to 30 μm. The pore diameter is 100 μm, the pore diameter is 280 μm for resin particles having an average particle diameter exceeding 30 to less than 90 μm, and the pore diameter is 400 μm for resin particles having an average particle diameter exceeding 90 μm.
The coefficient of variation (CV value) is a value calculated from the standard deviation (σ) and the average particle diameter (X) by the following equation.
CV value (%) = (σ / X) × 100
（ヘイズ）
光拡散フィルムのヘイズは、ＪＩＳ Ｋ７１３６に準じて測定され、具体的には、ヘーズメーター（日本電色工業株式会社製、型式：ＮＤＨ−２０００）を用いて測定する。
(Haze)
The haze of the light diffusion film is measured according to JIS K7136, and specifically, it is measured using a haze meter (Nippon Denshoku Industries Co., Ltd., model: NDH-2000).
（製造例１）
［第一工程］
内容積５Ｌのオートクレーブに、水２４００ｇおよび懸濁安定剤としてピロリン酸マグネシウム１６４ｇを仕込み、分散相とし、さらに界面活性剤としてラウリル硫酸ナトリウム０．８４ｇおよび重合禁止剤として亜硝酸ナトリウム０．２４ｇを加えた。
得られた分散相に、アクリル酸イソブチル７５６ｇ、開始剤としてベンゾイルパーオキサイド１２ｇ、連鎖移動剤としてオクチルメルカプタン１５ｇを混合した。
得られた混合物を、高速攪拌機（特殊機化工業株式会社、現 プライミクス株式会社製、型式：ＴＫホモミキサー）を用いて、回転数７５００ｒｐｍで１０分間攪拌してエマルジョンを得た。
得られた水性エマルジョンを８０℃で４時間反応させて、重量平均分子量Ｍｗ＝７万、平均粒子径７．４μｍの第一反応ポリマー（種粒子）の水性エマルジョンを得た。以下、「水性エマルジョン」を単に「エマルジョン」とも記載する。
(Production Example 1)
[First step]
An autoclave with an internal volume of 5 L was charged with 2400 g of water and 164 g of magnesium pyrophosphate as a suspension stabilizer, added as a dispersed phase, further added with 0.84 g of sodium lauryl sulfate as a surfactant and 0.24 g of sodium nitrite as a polymerization inhibitor. It was.
The obtained dispersed phase was mixed with 756 g of isobutyl acrylate, 12 g of benzoyl peroxide as an initiator, and 15 g of octyl mercaptan as a chain transfer agent.
The obtained mixture was stirred at a rotational speed of 7500 rpm for 10 minutes using a high-speed stirrer (Special Machine Industries Co., Ltd., current Primix Co., Ltd., model: TK homomixer) to obtain an emulsion.
The obtained aqueous emulsion was reacted at 80 ° C. for 4 hours to obtain an aqueous emulsion of the first reaction polymer (seed particles) having a weight average molecular weight Mw = 70,000 and an average particle diameter of 7.4 μm. Hereinafter, “aqueous emulsion” is also simply referred to as “emulsion”.
［第二工程］
内容積２Ｌのサスビーカーに、水４３２ｇ、界面活性剤としてラウリル硫酸ナトリウム０．０５ｇを加え、さらにメタクリル酸メチル１９４．４ｇ、エチレングリコールジメタクリレート２１７ｇ、ポリ（エチレングリコール−プロピレングリコール）モノメタクリレート（日油株式会社製、製品名：ブレンマー５０ＰＥＰ−３００、式１中、Ｒ１＝ＣＨ3、Ｒ２＝Ｃ2Ｈ4、Ｒ３＝Ｃ3Ｈ6、Ｒ４＝Ｈであり、ｍおよびｎは平均してｍ＝３．５およびｎ＝２．５の混合物である）２１．７ｇおよび開始剤としてアゾビスイソブチルニトリル（半減期温度６０℃）４．８ｇを混合した。
得られた混合物を、上記の高速攪拌機を用いて、回転数７５００ｒｐｍで１０分間攪拌してモノマー含有エマルジョンを得た。
[Second step]
To a suspension beaker having an internal volume of 2 L, 432 g of water and 0.05 g of sodium lauryl sulfate as a surfactant were added, and 194.4 g of methyl methacrylate, 217 g of ethylene glycol dimethacrylate, poly (ethylene glycol-propylene glycol) monomethacrylate (NOF) Product name: BLEMMER 50PEP-300, in formula 1, R1 = CH 3 , R2 = C 2 H 4 , R3 = C 3 H 6 , R4 = H, and m and n are m = on average 21.7 g (which is a mixture of 3.5 and n = 2.5) and 4.8 g of azobisisobutylnitrile (half-life temperature 60 ° C.) as initiator.
The obtained mixture was stirred for 10 minutes at a rotational speed of 7500 rpm using the above high-speed stirrer to obtain a monomer-containing emulsion.
［第三工程］
上記のオートクレーブ中の、第一工程で得られた第一反応ポリマーのエマルジョンを６０℃に冷却し、第二工程で得られたエマルジョンを１０分間掛けて連続滴下した。滴下終了後、６５℃で４時間重合させた。その後、スルファミン酸０．３ｇおよび直鎖アルキルベンゼンスルホン酸ソーダ６．３ｇを加え、１００℃に昇温し、この温度で１時間保持して反応を継続させた。次いで、３０℃に冷却し、塩酸を加えて、ピロリン酸マグネシウムを分解させた後、洗浄、脱水を行い、真空乾燥機にて６０℃で乾燥させ、平均粒子径８．６μｍの樹脂粒子を得た。
[Third step]
The emulsion of the first reaction polymer obtained in the first step in the autoclave was cooled to 60 ° C., and the emulsion obtained in the second step was continuously added dropwise over 10 minutes. After completion of the dropping, polymerization was carried out at 65 ° C. for 4 hours. Thereafter, 0.3 g of sulfamic acid and 6.3 g of linear alkylbenzene sulfonic acid soda were added, the temperature was raised to 100 ° C., and the reaction was continued at this temperature for 1 hour. Next, after cooling to 30 ° C. and adding hydrochloric acid to decompose magnesium pyrophosphate, washing and dehydration are performed, followed by drying at 60 ° C. in a vacuum dryer to obtain resin particles having an average particle size of 8.6 μm. It was.
（製造例２）
［第一工程］
内容積５Ｌのオートクレーブに、水２４００ｇおよび懸濁安定剤としてピロリン酸マグネシウム１６４ｇを仕込み、分散相とし、さらに界面活性剤としてラウリル硫酸ナトリウム０．８４ｇおよび重合禁止剤として亜硝酸ナトリウム０．２４ｇを加えた。
得られた分散相に、アクリル酸イソブチル７５６ｇ、開始剤としてベンゾイルパーオキサイド１２ｇ、連鎖移動剤としてオクチルメルカプタン３０ｇを混合した。
得られた混合物を、高速攪拌機（特殊機化工業株式会社、現 プライミクス株式会社製、型式：ＴＫホモミキサー）を用いて、回転数７５００ｒｐｍで１０分間攪拌してエマルジョンを得た。
得られた水性エマルジョンを８０℃で１０時間反応させて、重量平均分子量Ｍｗ＝３万、平均粒子径７．８μｍの第一反応ポリマー（種粒子）の水性エマルジョンを得た。
得られたエマルジョン用いて製造例１の［第二工程］および［第三工程］と同様の工程を経て、平均粒子径８．６μｍの樹脂粒子を得た。
(Production Example 2)
[First step]
An autoclave with an internal volume of 5 L was charged with 2400 g of water and 164 g of magnesium pyrophosphate as a suspension stabilizer, added as a dispersed phase, further added with 0.84 g of sodium lauryl sulfate as a surfactant and 0.24 g of sodium nitrite as a polymerization inhibitor. It was.
The obtained dispersed phase was mixed with 756 g of isobutyl acrylate, 12 g of benzoyl peroxide as an initiator, and 30 g of octyl mercaptan as a chain transfer agent.
The obtained mixture was stirred at a rotational speed of 7500 rpm for 10 minutes using a high-speed stirrer (Special Machine Industries Co., Ltd., current Primix Co., Ltd., model: TK homomixer) to obtain an emulsion.
The obtained aqueous emulsion was reacted at 80 ° C. for 10 hours to obtain an aqueous emulsion of the first reaction polymer (seed particles) having a weight average molecular weight Mw = 30,000 and an average particle diameter of 7.8 μm.
Using the obtained emulsion, resin particles having an average particle size of 8.6 μm were obtained through steps similar to [Second step] and [Third step] in Production Example 1.
（比較製造例１）
内容積５Ｌのオートクレーブに、水２４００ｇおよび懸濁安定剤としてピロリン酸マグネシウム１６４ｇを仕込み、分散相とし、さらに界面活性剤としてラウリル硫酸ナトリウム０．８４ｇおよび重合禁止剤として亜硝酸ナトリウム０．２４ｇを加えた。
得られた分散相に、アクリル酸イソブチル７３２ｇ、メタクリル酸メチル４２０ｇ、アリルメタクリレート１２ｇ、エチレングリコールジメタクリレート１５ｇ、開始剤としてベンゾイルパーオキサイド１２ｇおよびアゾビスイソブチルニトリル４．８ｇを混合した。
得られた混合物を、上記の高速攪拌を用いて、回転数７１００ｒｐｍで１０分間攪拌してエマルジョンを得た。
得られたエマルジョンを６０℃で４時間保持し重合させた。その後、スルファミン酸０．３ｇおよび直鎖アルキルベンゼンスルホン酸ソーダ６．３ｇを加え、１００℃に昇温し、この温度で１時間保持して反応を継続させた。次いで、３０℃に冷却し、塩酸を加えて、ピロリン酸マグネシウムを分解させた後、洗浄、脱水を行い、真空乾燥機にて６０℃で乾燥させ、平均粒子径８．３μｍの樹脂粒子を得た。
(Comparative Production Example 1)
An autoclave with an internal volume of 5 L was charged with 2400 g of water and 164 g of magnesium pyrophosphate as a suspension stabilizer, added as a dispersed phase, further added with 0.84 g of sodium lauryl sulfate as a surfactant and 0.24 g of sodium nitrite as a polymerization inhibitor. It was.
To the obtained dispersed phase, 732 g of isobutyl acrylate, 420 g of methyl methacrylate, 12 g of allyl methacrylate, 15 g of ethylene glycol dimethacrylate, 12 g of benzoyl peroxide as an initiator and 4.8 g of azobisisobutylnitrile were mixed.
The obtained mixture was stirred for 10 minutes at a rotational speed of 7100 rpm using the above high-speed stirring to obtain an emulsion.
The obtained emulsion was held at 60 ° C. for 4 hours for polymerization. Thereafter, 0.3 g of sulfamic acid and 6.3 g of linear alkylbenzene sulfonic acid soda were added, the temperature was raised to 100 ° C., and the reaction was continued at this temperature for 1 hour. Next, after cooling to 30 ° C. and adding hydrochloric acid to decompose magnesium pyrophosphate, washing and dehydration are carried out, followed by drying at 60 ° C. in a vacuum dryer to obtain resin particles having an average particle size of 8.3 μm. It was.
（比較製造例２：種粒子の重量平均分子量が大きい例）
［第一工程］
内容積５Ｌのオートクレーブに、水２４００ｇおよび懸濁安定剤としてピロリン酸マグネシウム１６４ｇを仕込み、分散相とし、さらに界面活性剤としてラウリル硫酸ナトリウム０．８４ｇおよび重合禁止剤として亜硝酸ナトリウム０．２４ｇを加えた。
得られた分散相に、アクリル酸イソブチル７５６ｇ、開始剤としてベンゾイルパーオキサイド１２ｇを混合した。
得られた混合物を、上記の高速攪拌機を用いて、回転数７５００ｒｐｍで１０分間攪拌してエマルジョンを得た。
得られたエマルジョンを７０℃で３時間反応させて、重量平均分子量Ｍｗ＝１５万、平均粒子径７．７μｍの第一反応ポリマーのエマルジョンを得た。
(Comparative Production Example 2: Example where seed particles have a large weight average molecular weight)
[First step]
An autoclave with an internal volume of 5 L was charged with 2400 g of water and 164 g of magnesium pyrophosphate as a suspension stabilizer, added as a dispersed phase, further added with 0.84 g of sodium lauryl sulfate as a surfactant and 0.24 g of sodium nitrite as a polymerization inhibitor. It was.
The obtained dispersed phase was mixed with 756 g of isobutyl acrylate and 12 g of benzoyl peroxide as an initiator.
The obtained mixture was stirred for 10 minutes at a rotational speed of 7500 rpm using the above high-speed stirrer to obtain an emulsion.
The obtained emulsion was reacted at 70 ° C. for 3 hours to obtain an emulsion of a first reaction polymer having a weight average molecular weight Mw = 150,000 and an average particle diameter of 7.7 μm.
［第二工程］
内容積２Ｌのサスビーカーに、水４３２ｇ、界面活性剤としてラウリル硫酸ナトリウム０．０５ｇを加え、さらにメタクリル酸メチル１９４．４ｇ、エチレングリコールジメタクリレート２１７ｇ、ポリ（エチレングリコーループロピレングリコール）モノメタクリレート（日油株式会社製、製品名：ブレンマー５０ＰＥＰ−３００、式１中、Ｒ１＝ＣＨ3、Ｒ２＝Ｃ2Ｈ4、Ｒ３＝Ｃ3Ｈ6、Ｒ４＝Ｈであり、ｍおよびｎは平均してｍ＝３．５およびｎ＝２．５の混合物である）２１．７ｇおよび開始剤としてアゾビスイソブチルニトリル４．８ｇを混合した。
得られた混合物を、上記の高速攪拌機を用いて、回転数７５００ｒｐｍで１０分間攪拌してエマルジョンを得た。
[Second step]
To a suspension beaker with an internal volume of 2 L, 432 g of water and 0.05 g of sodium lauryl sulfate as a surfactant were added, and 194.4 g of methyl methacrylate, 217 g of ethylene glycol dimethacrylate, poly (ethylene glycol-propylene glycol) monomethacrylate (NOF) Product name: BLEMMER 50PEP-300, in formula 1, R1 = CH 3 , R2 = C 2 H 4 , R3 = C 3 H 6 , R4 = H, and m and n are m = on average 21.7 g which is a mixture of 3.5 and n = 2.5) and 4.8 g of azobisisobutylnitrile as initiator.
The obtained mixture was stirred for 10 minutes at a rotational speed of 7500 rpm using the above high-speed stirrer to obtain an emulsion.
［第三工程］
上記のオートクレーブ中の、第一工程で得られた第一反応ポリマーのエマルジョンを６０℃に冷却し、第二工程で得られたエマルジョンを１０分間掛けて連続滴下した。滴下終了後、６５℃で４時間重合させた。その後、スルファミン酸０．３ｇおよび直鎖アルキルベンゼンスルホン酸ソーダ６．３ｇを加え、１００℃に昇温し、この温度で１時間保持して反応を継続させた。次いで、３０℃に冷却し、塩酸を加えて、ピロリン酸マグネシウムを分解させた後、洗浄、脱水を行い、真空乾燥機にて６０℃で乾燥させ、平均粒子径８．５μｍの樹脂粒子を得た。
[Third step]
The emulsion of the first reaction polymer obtained in the first step in the autoclave was cooled to 60 ° C., and the emulsion obtained in the second step was continuously added dropwise over 10 minutes. After completion of the dropping, polymerization was carried out at 65 ° C. for 4 hours. Thereafter, 0.3 g of sulfamic acid and 6.3 g of linear alkylbenzene sulfonic acid soda were added, the temperature was raised to 100 ° C., and the reaction was continued at this temperature for 1 hour. Next, after cooling to 30 ° C. and adding hydrochloric acid to decompose magnesium pyrophosphate, washing and dehydration were performed, followed by drying at 60 ° C. in a vacuum dryer to obtain resin particles having an average particle size of 8.5 μm. It was.
（比較製造例３）
［第一工程］
製造例１の第一工程と同様にして重量平均分子量Ｍｗ＝７万、平均粒子径７．４μｍの第一反応ポリマー（種粒子）の水性エマルジョンを得た。
［第二工程］（５０ＰＥＰなし）
内容積２Ｌのサスビーカーに、水４３２ｇ、界面活性剤としてラウリル硫酸ナトリウム０．０５ｇを加え、さらにメタクリル酸メチル１９４．４ｇ、エチレングリコールジメタクリレート２１７ｇおよび開始剤としてアゾビスイソブチルニトリル（半減期温度６０℃）４．８ｇを混合した。
得られた混合物を、上記の高速攪拌機を用いて、回転数７５００ｒｐｍで１０分間攪拌してモノマー含有エマルジョンを得た。
(Comparative Production Example 3)
[First step]
In the same manner as in the first step of Production Example 1, an aqueous emulsion of the first reaction polymer (seed particles) having a weight average molecular weight Mw = 70,000 and an average particle diameter of 7.4 μm was obtained.
[Second step] (without 50 PEP)
To a suspension beaker having an internal volume of 2 L, 432 g of water and 0.05 g of sodium lauryl sulfate as a surfactant were added, and 194.4 g of methyl methacrylate, 217 g of ethylene glycol dimethacrylate and azobisisobutylnitrile (half-life temperature 60 ° C.) as an initiator. ) 4.8 g was mixed.
The obtained mixture was stirred for 10 minutes at a rotational speed of 7500 rpm using the above high-speed stirrer to obtain a monomer-containing emulsion.
［第三工程］
上記のオートクレーブ中の、第一工程で得られた第一反応ポリマーのエマルジョンを６０℃に冷却し、第二工程で得られたエマルジョンを１０分間掛けて連続滴下した。滴下終了後、６５℃で４時間重合させた。その後、スルファミン酸０．３ｇおよび直鎖アルキルベンゼンスルホン酸ソーダ６．３ｇを加え、１００℃に昇温し、この温度で１時間保持して反応を継続させた。次いで、３０℃に冷却し、塩酸を加えて、ピロリン酸マグネシウムを分解させた後、洗浄、脱水を行い、真空乾燥機にて６０℃で乾燥させ、平均粒子径８．５μｍの樹脂粒子を得た。
[Third step]
The emulsion of the first reaction polymer obtained in the first step in the autoclave was cooled to 60 ° C., and the emulsion obtained in the second step was continuously added dropwise over 10 minutes. After completion of the dropping, polymerization was carried out at 65 ° C. for 4 hours. Thereafter, 0.3 g of sulfamic acid and 6.3 g of linear alkylbenzene sulfonic acid soda were added, the temperature was raised to 100 ° C., and the reaction was continued at this temperature for 1 hour. Next, after cooling to 30 ° C. and adding hydrochloric acid to decompose magnesium pyrophosphate, washing and dehydration were performed, followed by drying at 60 ° C. in a vacuum dryer to obtain resin particles having an average particle size of 8.5 μm. It was.
（実施例１）
次にようにして、内部多層粒子を用いた光学フィルム、すなわち光拡散層を備えた光拡散フィルムを製造した。
製造例１で得られた樹脂粒子１００重量部とアクリルバインダー（三菱レイヨン株式会社製、製品名：ダイヤナールＬＲ−１０２）１４０重量部とを混合した。得られた混合物に、重量比１：１のトルエンとメチルエチルケトンとの混合溶剤２６０重量部を添加・混合して分散液２．５ｇを得た。
得られた分散液を、遠心攪拌機（ＴＨＩＮＫＹ製、型式：ＡＲ−１００）を用いて３分間攪拌し、その後、３時間放置した。
次いで、放置後の分散液に、硬化剤（旭化成ケミカルズ株式会社製、製品名：デュラネートＴＫＡ−１００）３０重量部を添加して、再び上記の遠心攪拌機を用いて３分間攪拌した。
次いで、攪拌後の分散液を、７５μｍのコーターを用いてＰＥＴフィルム上に塗布し、７０℃に保った乾燥機にて１時間乾燥して、光拡散層を備えた光拡散フィルムを得た。
得られた光拡散フィルムのヘイズを測定した。
Example 1
Next, an optical film using internal multilayer particles, that is, a light diffusion film provided with a light diffusion layer was produced.
100 parts by weight of the resin particles obtained in Production Example 1 and 140 parts by weight of an acrylic binder (manufactured by Mitsubishi Rayon Co., Ltd., product name: Dianal LR-102) were mixed. 260 parts by weight of a mixed solvent of toluene and methyl ethyl ketone having a weight ratio of 1: 1 was added to and mixed with the obtained mixture to obtain 2.5 g of a dispersion.
The obtained dispersion was stirred for 3 minutes using a centrifugal stirrer (manufactured by THINKY, model: AR-100), and then allowed to stand for 3 hours.
Next, 30 parts by weight of a curing agent (manufactured by Asahi Kasei Chemicals Corporation, product name: Duranate TKA-100) was added to the dispersion after standing, and the mixture was again stirred for 3 minutes using the above centrifugal stirrer.
Next, the dispersion after stirring was applied onto a PET film using a 75 μm coater and dried for 1 hour in a drier kept at 70 ° C. to obtain a light diffusion film provided with a light diffusion layer.
The haze of the obtained light diffusion film was measured.
（比較例１）
製造例１で得られた樹脂粒子の代わりに比較製造例１で得られた樹脂粒子を用いること以外は実施例１と同様にして、光拡散層を備えた光拡散フィルムを得、そのヘイズを測定した。
(Comparative Example 1)
A light diffusing film provided with a light diffusing layer was obtained in the same manner as in Example 1 except that the resin particles obtained in Comparative Production Example 1 were used instead of the resin particles obtained in Production Example 1, and the haze was determined. It was measured.
（比較例２）
製造例１で得られた樹脂粒子の代わりに比較製造例２で得られた樹脂粒子を用いること以外は実施例１と同様にして、光拡散層を備えた光拡散フィルムを得、そのヘイズを測定した。
(Comparative Example 2)
A light diffusing film provided with a light diffusion layer was obtained in the same manner as in Example 1 except that the resin particles obtained in Comparative Production Example 2 were used instead of the resin particles obtained in Production Example 1, and the haze was determined. It was measured.
（比較例３）
製造例１で得られた樹脂粒子の代わりに比較製造例３で得られた樹脂粒子を用いること以外は実施例１と同様にして、光拡散層を備えた光拡散フィルムを得、そのヘイズを測定した。
(Comparative Example 3)
A light diffusing film provided with a light diffusion layer was obtained in the same manner as in Example 1 except that the resin particles obtained in Comparative Production Example 3 were used instead of the resin particles obtained in Production Example 1, and the haze was determined. It was measured.
製造例１〜２および比較製造例１〜３ならびにそれらに対応する実施例１〜２および比較例１〜３において得られた結果を、それらに用いた材料や条件と共に表１〜２に示す。
また、製造例１および比較製造例１の光拡散剤用粒子の（ａ）走査型電子顕微鏡（ＳＥＭ）写真および（ｂ）透過型電子顕微鏡(ＴＥＭ)写真をそれぞれ図１〜２に示す。
The results obtained in Production Examples 1 and 2 and Comparative Production Examples 1 to 3 and Examples 1 and 2 and Comparative Examples 1 to 3 corresponding thereto are shown in Tables 1 and 2 together with the materials and conditions used for them.
Moreover, the (a) scanning electron microscope (SEM) photograph and (b) transmission electron microscope (TEM) photograph of the light diffusing agent particles of Production Example 1 and Comparative Production Example 1 are shown in FIGS.
表１の結果から、本発明の光拡散剤用粒子およびそれを含む表面層を備えた光拡散フィルム（製造例１〜２および実施例１〜２）が光拡散性能に優れていることがわかる。
また、図１によれば、本発明の光拡散剤用粒子はその内部に種粒子に由来するポリマーと３種のモノマー由来のポリマーとが共存して特殊な内部構造（微細な相分離構造＝ミクロ相分離構造）を有していること、粒子表面に凹凸を有していることがわかる。一方、このような光拡散剤用粒子の状態は、図２の従来の光拡散剤用粒子では確認できない。
From the results in Table 1, it can be seen that the light diffusing film (Production Examples 1 and 2 and Examples 1 and 2) provided with the particles for light diffusing agent of the present invention and the surface layer containing the same are excellent in light diffusing performance. .
In addition, according to FIG. 1, the light diffusing agent particles of the present invention have a special internal structure (fine phase separation structure = a mixture of a polymer derived from seed particles and a polymer derived from three types of monomers in the interior thereof. It can be seen that it has a microphase separation structure and has irregularities on the particle surface. On the other hand, such a state of the light diffusing agent particles cannot be confirmed with the conventional light diffusing agent particles shown in FIG.
Claims (7)
で表される界面活性能を有するアクリレートモノマーおよび単官能アルキル（メタ）アクリレートモノマー（但し、前記式の界面活性能を有するアクリレートモノマーを除く）の３種のモノマーを添加して、前記非架橋アクリル系樹脂種粒子に前記３種のモノマーを吸収および重合させて、前記非架橋アクリル系樹脂種粒子に由来するポリマーと前記３種のモノマー由来のポリマーとが粒子内部でミクロ相分離構造を有する光拡散剤用粒子を得ることを特徴とする光拡散剤用粒子の製造方法。 In an aqueous emulsion in which non-crosslinked acrylic resin seed particles having a weight average molecular weight Mw of 20,000 to 80,000 are dispersed, a polyfunctional vinyl monomer, the following formula:
The non-crosslinked acrylic is added by adding three types of monomers, an acrylate monomer having a surface active ability and a monofunctional alkyl (meth) acrylate monomer (excluding an acrylate monomer having a surface active ability of the above formula). The resin having the three types of monomers absorbed and polymerized in the resin-based resin particles so that the polymer derived from the non-crosslinked acrylic resin seed particles and the polymer derived from the three monomers have a microphase separation structure inside the particles. A method for producing particles for a light diffusing agent, comprising obtaining particles for a diffusing agent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105555840A (en) * | 2013-08-30 | 2016-05-04 | 积水化成品工业株式会社 | Resin particle group and method for manufacturing same |
| JPWO2015186615A1 (en) * | 2014-06-02 | 2017-04-20 | 株式会社トクヤマ | Light diffusing agent and light diffusing composition using the same |
| CN109851698A (en) * | 2018-03-22 | 2019-06-07 | 天津城建大学 | A kind of surface has the ABA type colloidal solid and preparation method thereof of multiple property |
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2011
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105555840A (en) * | 2013-08-30 | 2016-05-04 | 积水化成品工业株式会社 | Resin particle group and method for manufacturing same |
| JPWO2015029483A1 (en) * | 2013-08-30 | 2017-03-02 | 積水化成品工業株式会社 | Resin particle group and method for producing the same |
| CN105555840B (en) * | 2013-08-30 | 2020-10-30 | 积水化成品工业株式会社 | Resin particle group and method for producing same |
| JPWO2015186615A1 (en) * | 2014-06-02 | 2017-04-20 | 株式会社トクヤマ | Light diffusing agent and light diffusing composition using the same |
| CN109851698A (en) * | 2018-03-22 | 2019-06-07 | 天津城建大学 | A kind of surface has the ABA type colloidal solid and preparation method thereof of multiple property |
| CN109851698B (en) * | 2018-03-22 | 2021-05-07 | 天津城建大学 | A kind of ABA-type colloidal particle with multiple properties on the surface and preparation method thereof |
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