JPS60170604A - 超微粒子既架橋ポリマ−ラテツクスの製造方法 - Google Patents
超微粒子既架橋ポリマ−ラテツクスの製造方法Info
- Publication number
- JPS60170604A JPS60170604A JP59027452A JP2745284A JPS60170604A JP S60170604 A JPS60170604 A JP S60170604A JP 59027452 A JP59027452 A JP 59027452A JP 2745284 A JP2745284 A JP 2745284A JP S60170604 A JPS60170604 A JP S60170604A
- Authority
- JP
- Japan
- Prior art keywords
- polymer latex
- polymerization
- monomer
- ultrafine
- 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.)
- Granted
Links
- 239000004816 latex Substances 0.000 title claims abstract description 49
- 229920000126 latex Polymers 0.000 title claims abstract description 49
- 229920006037 cross link polymer Polymers 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 13
- -1 sulfoxy compound Chemical class 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 4
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000007717 redox polymerization reaction Methods 0.000 claims abstract description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 159000000000 sodium salts Chemical class 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- NNOPYZMQAAGVBG-UHFFFAOYSA-N 2-[3-carboxypropanoyl(octadecyl)amino]butanedioic acid Chemical compound CCCCCCCCCCCCCCCCCCN(C(CC(O)=O)C(O)=O)C(=O)CCC(O)=O NNOPYZMQAAGVBG-UHFFFAOYSA-N 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 239000011882 ultra-fine particle Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XNYGYPGNRPBPPY-UHFFFAOYSA-N C(=O)(O)C(CC(=O)O)N(C(C(CC(=O)O)S(=O)(=O)O)=O)CCCCCCCCCCCCCCCCCC.[Na].[Na].[Na].[Na] Chemical compound C(=O)(O)C(CC(=O)O)N(C(C(CC(=O)O)S(=O)(=O)O)=O)CCCCCCCCCCCCCCCCCC.[Na].[Na].[Na].[Na] XNYGYPGNRPBPPY-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XPNLOZNCOBKRNJ-UHFFFAOYSA-N ethyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C=C.COC(=O)C(C)=C XPNLOZNCOBKRNJ-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- IOLYDULOQSPURX-UHFFFAOYSA-J tetrasodium 2-octadecyl-2-sulfobutanedioate Chemical compound CCCCCCCCCCCCCCCCCCC(CC(=O)[O-])(C(=O)[O-])S(=O)(=O)O.CCCCCCCCCCCCCCCCCCC(CC(=O)[O-])(C(=O)[O-])S(=O)(=O)O.[Na+].[Na+].[Na+].[Na+] IOLYDULOQSPURX-UHFFFAOYSA-J 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 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 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 229940095095 2-hydroxyethyl acrylate Drugs 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
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- TXHIDIHEXDFONW-UHFFFAOYSA-N benzene;propan-2-one Chemical compound CC(C)=O.C1=CC=CC=C1 TXHIDIHEXDFONW-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
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polymerisation Methods In General (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59027452A JPS60170604A (ja) | 1984-02-16 | 1984-02-16 | 超微粒子既架橋ポリマ−ラテツクスの製造方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59027452A JPS60170604A (ja) | 1984-02-16 | 1984-02-16 | 超微粒子既架橋ポリマ−ラテツクスの製造方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60170604A true JPS60170604A (ja) | 1985-09-04 |
| JPH0370724B2 JPH0370724B2 (enExample) | 1991-11-08 |
Family
ID=12221509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59027452A Granted JPS60170604A (ja) | 1984-02-16 | 1984-02-16 | 超微粒子既架橋ポリマ−ラテツクスの製造方法 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60170604A (enExample) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4943612A (en) * | 1986-12-06 | 1990-07-24 | Lion Corporation | Ultra-fine particulated polymer latex and composition containing the same |
| US10590300B2 (en) * | 2013-12-19 | 2020-03-17 | Toray Films Europe | Composition for coating polymer films, coating process and composite materials obtained |
-
1984
- 1984-02-16 JP JP59027452A patent/JPS60170604A/ja active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4943612A (en) * | 1986-12-06 | 1990-07-24 | Lion Corporation | Ultra-fine particulated polymer latex and composition containing the same |
| US10590300B2 (en) * | 2013-12-19 | 2020-03-17 | Toray Films Europe | Composition for coating polymer films, coating process and composite materials obtained |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0370724B2 (enExample) | 1991-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3787522A (en) | Acrylate polymer particles comprising a core,an outer shell,and an intermediate layer | |
| CA1113644A (en) | Thermosetting resin, and its production and use | |
| US3992486A (en) | Process for altering appearance of polymer by incorporating therein crosslinked particulate polymers prepared by endopolymerization | |
| US3914338A (en) | Opalescent methylmethacrylate polymer bodies | |
| CA2095738A1 (en) | Coated inorganic particles | |
| BRPI0903407A2 (pt) | partìcula polimérica e métodos para formar uma partìcula polimérica e para proporcionar opacidade a uma composição seca | |
| JPS61223015A (ja) | 複合樹脂粒子ならびに塗料用樹脂組成物 | |
| CN114015000A (zh) | 一种嵌段共聚物胶乳的制备方法 | |
| CN106699957A (zh) | 一种羟基丙烯酸乳液的制备方法 | |
| JPH0370725B2 (enExample) | ||
| JPS62119271A (ja) | 塩基性複合樹脂粒子、その製法ならびに塗料用樹脂組成物 | |
| JP2003183410A (ja) | 微粒子集合体およびその製造方法 | |
| JP3637794B2 (ja) | メタクリル酸メチル系重合体ビーズの製造方法 | |
| CA2304054C (en) | Materials which can be thermally coated with a polymerizable component | |
| JPH0370724B2 (enExample) | ||
| JPS62177007A (ja) | 高濃度反応性ミクロゲルの製造方法 | |
| JP3149487B2 (ja) | メタアクリル系樹脂粒子の製造方法 | |
| JPH0791348B2 (ja) | 架橋ポリマー粒子の製造方法 | |
| CN110642982B (zh) | 一种核壳结构高抗拉酰胺苯环类乳液聚合物制备方法 | |
| CN102936305A (zh) | 悬浮聚合制备支化聚合物的方法 | |
| JP3633327B2 (ja) | メタクリル酸メチル系重合体ビーズの製造法 | |
| CN116410394A (zh) | 一种水性聚（甲基）丙烯酸自消光树脂及免罩面自消光多彩涂料 | |
| Pavlyuchenko et al. | Submicron sized hollow polymer particles: preparation and properties | |
| JPH01182313A (ja) | 架橋微粒子重合体の製造方法 | |
| CN113845616A (zh) | 一种pmma共聚功能树脂及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |