JPH04335052A - Powder composition and its production - Google Patents
Powder composition and its productionInfo
- Publication number
- JPH04335052A JPH04335052A JP13332991A JP13332991A JPH04335052A JP H04335052 A JPH04335052 A JP H04335052A JP 13332991 A JP13332991 A JP 13332991A JP 13332991 A JP13332991 A JP 13332991A JP H04335052 A JPH04335052 A JP H04335052A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- powder
- latex
- graft copolymer
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 103
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 58
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 43
- 239000000314 lubricant Substances 0.000 claims abstract description 23
- 229920001971 elastomer Polymers 0.000 claims abstract description 20
- 230000009477 glass transition Effects 0.000 claims abstract description 14
- 239000004816 latex Substances 0.000 claims description 64
- 229920000126 latex Polymers 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 230000001112 coagulating effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 abstract description 5
- 238000005303 weighing Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 24
- -1 vinyl compound Chemical class 0.000 description 24
- 239000002245 particle Substances 0.000 description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 11
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010559 graft polymerization reaction Methods 0.000 description 5
- 229920000642 polymer Polymers 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229920003244 diene elastomer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BIOCRZSYHQYVSG-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-diethylethanamine Chemical compound CCN(CC)CCC1=CC=C(C=C)C=C1 BIOCRZSYHQYVSG-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000008360 acrylonitriles Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 2
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 2
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical group CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- KCFXNGDHQPMIAQ-UHFFFAOYSA-N 1-(4-methylphenyl)pyrrole-2,5-dione Chemical compound C1=CC(C)=CC=C1N1C(=O)C=CC1=O KCFXNGDHQPMIAQ-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-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
- QZLAEIZEPJAELS-UHFFFAOYSA-N 2,4,4-trimethylpentane-2-thiol Chemical compound CC(C)(C)CC(C)(C)S QZLAEIZEPJAELS-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-UHFFFAOYSA-N 2-bromoethenylbenzene Chemical compound BrC=CC1=CC=CC=C1 YMOONIIMQBGTDU-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- WPDAVTSOEQEGMS-UHFFFAOYSA-N 9,10-dihydroanthracene Chemical compound C1=CC=C2CC3=CC=CC=C3CC2=C1 WPDAVTSOEQEGMS-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- GBJVVSCPOBPEIT-UHFFFAOYSA-N AZT-1152 Chemical compound N=1C=NC2=CC(OCCCN(CC)CCOP(O)(O)=O)=CC=C2C=1NC(=NN1)C=C1CC(=O)NC1=CC=CC(F)=C1 GBJVVSCPOBPEIT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- FVCPXLWAKNJIKK-UHFFFAOYSA-N Dimexano Chemical compound COC(=S)SSC(=S)OC FVCPXLWAKNJIKK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 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
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、ABS樹脂、MBS樹
脂などに代表されるグラフト共重合体粉体の粉体特性を
改良した粉体組成物およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder composition with improved powder characteristics of a graft copolymer powder typified by ABS resin, MBS resin, etc., and a method for producing the same.
【0002】0002
【従来の技術】近年、粉体計量の自動化および輸送方式
の大型化によって省力化が進められており、これにとも
ない粉体自体のハンドリングの問題がクローズアップさ
れている。すなわち、粉体同士が貯蔵中に固まるという
ブロッキング現象や、ホッパー中に粉体が止まるという
ブリッジング現象、流動性不足による輸送ラインの詰ま
りなどのトラブルに対し、耐ブロッキング性、流動性お
よびかさ比重で代表される粉体特性の改良が強く要望さ
れている。2. Description of the Related Art In recent years, efforts have been made to save labor by automating powder weighing and increasing the size of transportation methods, and with this, the problem of handling the powder itself has been brought into focus. In other words, we have improved blocking resistance, fluidity, and bulk specific gravity to prevent problems such as blocking phenomenon where powders solidify together during storage, bridging phenomenon where powders get stuck in the hopper, and clogging of transportation lines due to lack of fluidity. There is a strong demand for improvements in the powder properties represented by .
【0003】この粉体特性を改良するための方法が、こ
れまで種々検討されている。例えば、グラフト共重合体
ラテックスを直接噴霧乾燥する方法、グラフト共重合体
ラテックスを気相凝固する方法などが挙げられる。しか
しながら、これらの方法では、充分な粉体特性の改良効
果がみられない。一方、滑剤などの添加剤を適量添加す
る方法も挙げられるが、この方法でも、充分な粉体特性
を改良できる効果は得られず、特に通常の工程でみられ
る乾燥工程後の加熱状態の樹脂粉体を風袋し、段積みに
保管される場合では、熱融着が先行し、耐ブロッキング
効果が充分発現されないという問題がある。[0003] Various methods have been studied to improve the powder properties. Examples include a method of directly spray drying the graft copolymer latex, a method of coagulating the graft copolymer latex in a vapor phase, and the like. However, these methods do not show a sufficient effect of improving powder properties. On the other hand, there is also a method of adding an appropriate amount of additives such as lubricants, but even this method does not have the effect of sufficiently improving the powder properties, especially when the resin is heated after the drying process that is seen in normal processes. When the powder is tared and stored in stacks, there is a problem that heat fusion occurs first and the anti-blocking effect is not sufficiently developed.
【0004】0004
【発明が解決しようとする課題】本発明は、前記従来技
術の課題を背景になされたもので、ブロッキング現象、
ブリッジング現象、輸送ライン中の詰まり現象などがな
く、その結果粉体計量の自動化、輸送方式の大型化など
の省力化が可能な、グラフト共重合体の粉体特性を改良
した粉体組成物およびその製造方法を提供することを目
的とする。SUMMARY OF THE INVENTION The present invention has been made against the background of the above-mentioned problems of the prior art, and solves the problem of blocking phenomenon,
A powder composition with improved powder characteristics of a graft copolymer that does not cause bridging phenomena or clogging phenomena in transportation lines, and as a result, can automate powder weighing and save labor such as increasing the size of transportation methods. The purpose is to provide a method for producing the same.
【0005】[0005]
【課題を解決するための手段】本発明は、ゴム質重合体
の含有量が30〜80重量%であるグラフト共重合体(
A)の粉体100重量部に対し、ガラス転移温度が70
〜170℃でかつ重量平均分子量が100万以下のビニ
ル系重合体(B)の粉体0.1〜10重量部、および滑
剤(C)0〜10重量部を主成分とする粉体組成物を提
供するものである。[Means for Solving the Problems] The present invention provides a graft copolymer (
For 100 parts by weight of powder A), the glass transition temperature is 70%.
A powder composition containing as main components 0.1 to 10 parts by weight of a vinyl polymer (B) powder at ~170°C and a weight average molecular weight of 1 million or less, and 0 to 10 parts by weight of a lubricant (C). It provides:
【0006】本発明の粉体組成物を構成するグラフト共
重合体(A)は、ゴム質重合体の存在下に、ビニル系単
量体をグラフト重合することによって得られる。このグ
ラフト重合は、好ましくは乳化重合である。乳化重合を
採用する場合、ゴム質重合体の中で、溶液重合あるいは
バルク重合により得られたものは、公知の方法で乳化し
、ラテックス状にして用いる。ここで、ゴム質重合体と
しては、例えばポリブタジエン、ポリイソプレン、スチ
レン−ブタジエンランダム共重合体、アクリロニトリル
−ブタジエン共重合体、スチレン−ブタジエンブロック
共重合体、ポリクロロプレンなどのジエン系ゴム質重合
体、該ジエン系ゴム質重合体の水素添加物、エチレン−
プロピレン−(ジエン)ゴム、アクリルゴムなどが挙げ
られる。ゴム質重合体としては、好ましくは乳化重合法
により得られるジエン系ゴム質重合体であり、さらに好
ましくは乳化重合法により得られるポリブタジエン、ス
チレン−ブタジエンランダム共重合体である。これらの
ゴム質重合体は、1種または2種以上で使用される。The graft copolymer (A) constituting the powder composition of the present invention is obtained by graft polymerizing a vinyl monomer in the presence of a rubbery polymer. This graft polymerization is preferably emulsion polymerization. When employing emulsion polymerization, among the rubbery polymers, those obtained by solution polymerization or bulk polymerization are emulsified by a known method and used in the form of latex. Here, examples of the rubbery polymer include diene rubbery polymers such as polybutadiene, polyisoprene, styrene-butadiene random copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, and polychloroprene; Hydrogenated product of the diene rubbery polymer, ethylene-
Examples include propylene (diene) rubber and acrylic rubber. The rubbery polymer is preferably a diene-based rubbery polymer obtained by emulsion polymerization, and more preferably polybutadiene or styrene-butadiene random copolymer obtained by emulsion polymerization. These rubbery polymers may be used alone or in combination of two or more.
【0007】また、グラフト重合に供されるビニル系単
量体としては、芳香族ビニル化合物、シアン化ビニル化
合物、(メタ)アクリル酸エステル、その他の共重合可
能な単量体が挙げられる。これらのビニル系単量体うち
、芳香族ビニル化合物としては、スチレン、t−ブチル
スチレン、α−メチルスチレン、p−メチルスチレン、
ジビニルベンゼン、1,1−ジフェニルスチレン、N,
N−ジエチル−p−アミノエチルスチレン、N,N−ジ
エチル−p−アミノエチルスチレン、ビニルピリジン、
ビニルキシレン、モノクロルスチレン、ジクロルスチレ
ン、モノブロムスチレン、フルオロスチレン、エチルス
チレン、ビニルナフタレンなどが挙げられ、特にスチレ
ン、α−メチルスチレンが好ましい。また、シアノ化ビ
ニル化合物としては、例えばアクリロニトリル、メタク
リロニトリルなどが挙げられ、これらは1種または2種
以上で使用される。シアン化ビニル化合物としては、特
にアクリロニトリルが好ましい。[0007] Vinyl monomers to be subjected to graft polymerization include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid esters, and other copolymerizable monomers. Among these vinyl monomers, aromatic vinyl compounds include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene,
Divinylbenzene, 1,1-diphenylstyrene, N,
N-diethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, vinylpyridine,
Examples include vinylxylene, monochlorostyrene, dichlorostyrene, monobromstyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, and styrene and α-methylstyrene are particularly preferred. Examples of the cyanated vinyl compound include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more. Acrylonitrile is particularly preferred as the vinyl cyanide compound.
【0008】さらに、(メタ)アクリル酸エステルとし
ては、メチルアクリレート、エチルアクリレート、プロ
ピルアクリレート、ブチルアクリレート、アミルアクリ
レート、ヘキシルアクリレート、オクチルアクリレート
、2−エチルヘキシルアクリレート、シクロヘキシルア
クリレート、ドデシルアクリレート、オクタデシルアク
リレート、フェニルアクリレート、ベンジルアクリレー
トなどのアクリル酸エステル;メチルメタクリレート、
エチルメタクリレート、プロピルメタクリレート、ブチ
ルメタクリレート、アミルメタクリレート、ヘキシルメ
タクリレート、オクチルメタクリレート、2−エチルヘ
キシルメタクリレート、シクロヘキシルメタクリレート
、ドデシルメタクリレート、オクタデシルメタクリレー
ト、フェニルメタクリレート、ベンジルメタクリレート
などが挙げられ、好ましくはメチルメタクリレートであ
る。Furthermore, (meth)acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, and phenyl acrylate. Acrylic acid esters such as acrylate and benzyl acrylate; methyl methacrylate,
Examples include ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate, with methyl methacrylate being preferred.
【0009】さらに、その他の共重合可能な単量体とし
ては、無水マレイン酸、無水イタコン酸、無水シトラコ
ン酸などの不飽和酸無水物;アクリル酸、メタクリル酸
などの不飽和酸;マレイミド、N−メチルマレイミド、
N−ブチルマレイミド、N−(p−メチルフェニル)マ
レイミド、N−フェニルマレイミド、N−シクロヘキシ
ルマレイミドなどのマレイミド化合物;グリシジルメタ
クリレートなどのエポキシ化合物などが挙げられる。な
お、マレイミド化合物は、例えば無水マレイン酸を共重
合させ、これをアニリンなどでイミド化したものも含ま
れる。以上のビニル系単量体は、1種単独であるいは2
種以上を併用することができる。Furthermore, other copolymerizable monomers include unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N - methylmaleimide,
Examples include maleimide compounds such as N-butylmaleimide, N-(p-methylphenyl)maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; and epoxy compounds such as glycidyl methacrylate. Note that the maleimide compound includes, for example, one obtained by copolymerizing maleic anhydride and imidizing this with aniline or the like. The above vinyl monomers may be used alone or in combination.
More than one species can be used together.
【0010】好ましいビニル系単量体としては、下記の
■〜■いずれかの組み合わせが挙げられる。
■芳香族ビニル化合物/シアン化ビニル化合物=40〜
95/5〜60重量%
■芳香族ビニル化合物/(メタ)アクリル酸エステル=
10〜95/5〜90重量%
■芳香族ビニル化合物/(メタ)アクリル酸エステル/
シアン化ビニル化合物=10〜95/4〜90/1〜6
0重量%[0010] Preferred vinyl monomers include any of the following combinations (1) to (2). ■Aromatic vinyl compound/vinyl cyanide compound = 40~
95/5 to 60% by weight ■Aromatic vinyl compound/(meth)acrylic acid ester=
10-95/5-90% by weight ■Aromatic vinyl compound/(meth)acrylic acid ester/
Vinyl cyanide compound = 10-95/4-90/1-6
0% by weight
【0011】前記ゴム質重合体およびグラフト共重合体
(A)を乳化重合法で製造するには、ゴム質重合体を構
成する単量体、あるいはゴム質重合体の存在下にビニル
系単量体に、重合開始剤、連鎖移動剤、乳化剤などを加
えたものを攪拌しながら、通常、5〜98℃で乳化重合
することにより得られる。ここで、重合開始剤としては
、クメンハイドロパーオキサイド、ジイソプロピルベン
ゼンハイドロパーオキサイド、パラメンタンハイドロパ
ーオキサイドなどの有機ハイドロパーオキサイド類と含
糖ピロリン酸処方もしくはスルホキシレート処方などの
還元剤との組合せによるレドックス系、あるいは過硫酸
塩、アゾビスイソブチロニトリル、ベンゾイルパーオキ
サイドなどの過酸化物が使用される。[0011] In order to produce the rubbery polymer and graft copolymer (A) by an emulsion polymerization method, monomers constituting the rubbery polymer or vinyl monomers are added in the presence of the rubbery polymer. It is usually obtained by emulsion polymerization at 5 to 98°C while stirring a mixture of a polymerization initiator, a chain transfer agent, an emulsifier, and the like. Here, the polymerization initiator is a combination of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide, and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation. redox systems, or peroxides such as persulfates, azobisisobutyronitrile, and benzoyl peroxide are used.
【0012】また、連鎖移動剤としては、n−ヘキシル
メルカプタン、n−オクチルメルカプタン、t−オクチ
ルメルカプタン、t−ドデシルメルカプタン、n−ドデ
シルメルカプタン、n−ステアリルメルカプタンなどの
メルカプタン類、クロロホルム、ブロモホルム、四塩化
炭素、四臭化炭素などの炭化水素類、ジメチルキサント
ゲンジサルファイド、ジイソプロピルキサントゲンジサ
ルファイドなどのキサントゲン類、α−メチルスチレン
ダイマー、9,10−ジヒドロアントラセン、1,4−
シクロヘキジエン、1,4−ヘキサジエン、2,5−ジ
ヒドロフランなどが挙げられる。As chain transfer agents, mercaptans such as n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, t-dodecylmercaptan, n-dodecylmercaptan, and n-stearylmercaptan, chloroform, bromoform, and Hydrocarbons such as carbon chloride and carbon tetrabromide, xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide, α-methylstyrene dimer, 9,10-dihydroanthracene, 1,4-
Examples include cyclohexadiene, 1,4-hexadiene, 2,5-dihydrofuran, and the like.
【0013】さらに、乳化剤としては、一般に用いられ
る乳化剤が使用できるが、ロジン酸、オレイン酸、ラウ
リル酸、ステアリン酸もしくはアルケニルコハク酸など
の脂肪酸のナトリウム塩またはカリウム塩、ドデシルベ
ンゼンスルホン酸ナトリウムなどのアルキルアリルスル
ホン酸塩、ジアルキルスルホコハク酸などの、アニオン
性界面活性剤が好ましい。なお、単量体の添加方法は、
単量体の一括添加重合、連続添加重合、多段階重合など
の一般に知られている乳化重合法を採用することができ
、乳化剤も単量体と同様にして添加することができる。Further, as the emulsifier, commonly used emulsifiers can be used, but sodium salts or potassium salts of fatty acids such as rosin acid, oleic acid, lauric acid, stearic acid or alkenylsuccinic acid, sodium dodecylbenzenesulfonate, etc. Anionic surfactants are preferred, such as alkylaryl sulfonates, dialkyl sulfosuccinic acids, and the like. The method of adding the monomer is as follows:
Generally known emulsion polymerization methods such as bulk addition polymerization, continuous addition polymerization, and multistage polymerization of monomers can be employed, and the emulsifier can also be added in the same manner as the monomers.
【0014】このようにして得られるグラフト共重合体
(A)中のゴム質重合体の含有量は、30〜80重量%
、好ましくは30〜70重量%である。(A)成分中の
ゴム質重合体の含有量が30重量%未満では、(A)成
分自体が充分な粉体特性を有しており、本発明の組成物
を調製する必要はない。一方、80重量%を超えると、
後記(B)〜(C)成分を加えたとしても、粉体特性が
充分な組成物が得られない。The content of the rubbery polymer in the graft copolymer (A) thus obtained is 30 to 80% by weight.
, preferably 30 to 70% by weight. When the content of the rubbery polymer in component (A) is less than 30% by weight, component (A) itself has sufficient powder properties and there is no need to prepare the composition of the present invention. On the other hand, if it exceeds 80% by weight,
Even if components (B) to (C) described below are added, a composition with sufficient powder characteristics cannot be obtained.
【0015】なお、グラフト共重合体(A)の好ましい
グラフト率は、10重量%以上、好ましくは20重量%
以上であり、グラフト率がこの範囲にあると、一段と優
れた本発明の目的とするものが得られる。ここで、グラ
フト共重合体(A)のグラフト率は、次の方法で求めた
値である。すなわち、グラフト共重合体(A)を20重
量倍のメチルエチルケトンに投入し、25℃×48時間
攪拌し、次いで遠心分離機を用いて不溶分(乾燥重量=
W)および可溶分(乾燥重量=X)を採取し、下記式よ
り求めた。
グラフト率(%)=〔(W−R)/R〕×100(式中
、Rは重合処方より求めたグラフト前のゴム質重合体の
重量である。)[0015] The preferable graft ratio of the graft copolymer (A) is 10% by weight or more, preferably 20% by weight.
This is the above, and when the grafting ratio is within this range, even more excellent objects of the present invention can be obtained. Here, the graft ratio of the graft copolymer (A) is a value determined by the following method. That is, the graft copolymer (A) was added to 20 times the weight of methyl ethyl ketone, stirred at 25°C for 48 hours, and then centrifuged to remove the insoluble matter (dry weight =
W) and soluble content (dry weight = X) were collected and determined from the following formula. Grafting rate (%) = [(WR)/R] x 100 (wherein, R is the weight of the rubbery polymer before grafting determined from the polymerization recipe.)
【0016】次に、本発明の粉体組成物を構成するビニ
ル系重合体(B)は、前記グラフト共重合体(A)のグ
ラフト重合に使用されるビニル系単量体と同様のものを
、乳化重合法、懸濁重合法、好ましくは乳化重合法によ
り重合することによって得られる。(B)成分を製造す
る際の乳化重合法は、(A)成分を調製する際の乳化重
合法と同様である。Next, the vinyl polymer (B) constituting the powder composition of the present invention is a vinyl monomer similar to the vinyl monomer used in the graft polymerization of the graft copolymer (A). , emulsion polymerization, suspension polymerization, preferably emulsion polymerization. The emulsion polymerization method used to produce component (B) is the same as the emulsion polymerization method used to prepare component (A).
【0017】なお、ビニル系重合体(B)を構成するビ
ニル系単量体の種類は、前記グラフト共重合体(A)の
グラフト重合に供されるビニル系単量体の種類によって
適宜選択することが好ましい。例えば、グラフト共重合
体(A)を製造する際のビニル系単量体が芳香族ビニル
化合物およびシアン化ビニル化合物である場合には、(
B)成分を構成するビニル系単量体としては、芳香族ビ
ニル化合物、シアン化ビニル化合物および(メタ)アク
リル酸エステルの群から選ばれた少なくとも2種の単量
体である。また、グラフト共重合体(A)を製造する際
のビニル系単量体が芳香族ビニル化合物および(メタ)
アクリル酸エステルである場合には、(B)成分を構成
するビニル系単量体としては、(メタ)アクリル酸エス
テル、あるいは(メタ)アクリル酸エステルおよび芳香
族ビニル化合物が好ましい。これらのビニル系単量体の
うち、芳香族ビニル化合物としては、スチレン、t−ブ
チルスチレン、α−メチルスチレン、p−メチルスチレ
ン、ジビニルベンゼン、1,1−ジフェニルスチレン、
N,N−ジエチル−p−アミノエチルスチレン、ビニル
ピリジン、ビニルキシレン、モノクロルスチレン、ジク
ロルスチレン、モノブロムスチレン、フルオロスチレン
、エチルスチレン、ビニルナフタレンなどが挙げられ、
これらは1種または2種以上で使用される。なかでも、
特にスチレン、α−メチルスチレンが好ましい。また、
シアン化ビニル化合物としては、例えばアクリロニトリ
ル、メタクリロニトリルなどが挙げられ、これらは1種
または2種以上で使用される。シアン化ビニル化合物と
しては、特にアクリロニトリルが好ましい。さらに、(
メタ)アクリル酸エステルとしては、メチルメタクリレ
ート、t−ブチルメタクリレート、sec−ブチルメタ
クリレート、2−ヒドロキシエチルメタクリレート、イ
ソボルニルアクリレート、2−ナフチルアクリレートな
どが挙げられ、これらは1種または2種以上で使用され
る。(メタ)アクリル酸エステルとしては、メチルメタ
クリレートが好ましい。[0017] The type of vinyl monomer constituting the vinyl polymer (B) is appropriately selected depending on the type of vinyl monomer used in the graft polymerization of the graft copolymer (A). It is preferable. For example, when the vinyl monomers used to produce the graft copolymer (A) are an aromatic vinyl compound and a vinyl cyanide compound, (
The vinyl monomers constituting component B) are at least two monomers selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylic acid esters. Furthermore, the vinyl monomer used in producing the graft copolymer (A) is an aromatic vinyl compound and (meth)
In the case of an acrylic ester, the vinyl monomer constituting component (B) is preferably a (meth)acrylic ester or a (meth)acrylic ester and an aromatic vinyl compound. Among these vinyl monomers, aromatic vinyl compounds include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene,
N,N-diethyl-p-aminoethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc.
These may be used alone or in combination of two or more. Among them,
Particularly preferred are styrene and α-methylstyrene. Also,
Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more. Acrylonitrile is particularly preferred as the vinyl cyanide compound. moreover,(
Examples of the meth)acrylic acid ester include methyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate, 2-hydroxyethyl methacrylate, isobornyl acrylate, and 2-naphthyl acrylate, and these may be used alone or in combination of two or more. used. As the (meth)acrylic acid ester, methyl methacrylate is preferred.
【0018】このビニル系重合体(B)のガラス転移温
度は、70〜170℃、好ましくは80〜120℃であ
る。ガラス転移温度が70℃未満では、充分な粉体特性
が得られず、一方170℃を超えると、凝固が困難とな
り超微粉の発生あるいは凝固が不充分となる場合がある
。ここで、ビニル系重合体(B)のガラス転移温度の調
整は、用いられるビニル系単量体の種類、量を適宜選ぶ
ことにより容易に達成することができる。また、ビニル
系重合体(B)のガラス転移温度の測定は、例えばDS
C測定装置〔セイコー電子(株)製、SSC/580D
S〕によって測定することができる。The glass transition temperature of the vinyl polymer (B) is 70 to 170°C, preferably 80 to 120°C. If the glass transition temperature is less than 70°C, sufficient powder characteristics cannot be obtained, while if it exceeds 170°C, coagulation becomes difficult and ultrafine powder may be generated or coagulation may be insufficient. Here, adjustment of the glass transition temperature of the vinyl polymer (B) can be easily achieved by appropriately selecting the type and amount of the vinyl monomer used. Furthermore, the glass transition temperature of the vinyl polymer (B) can be measured using, for example, DS
C measurement device [Seiko Electronics Co., Ltd., SSC/580D
S].
【0019】また、ビニル系重合体(B)の重量平均分
子量は、100万以下、好ましくは3〜90万であり、
100万を超えると、得られる組成物を用いて成形した
場合にフィッシュアイが生じるので好ましくない。この
重量平均分子量の調整は、連鎖移動剤あるいは重合開始
剤量などの調整により容易に達成することができる。こ
こで、重量平均分子量は、例えば東ソー(株)製の高速
液体クロマトグラフHLC−802A(キャリヤ液=テ
トラヒドロフラン)を用い、ポリスチレン換算で求めた
値である。Furthermore, the weight average molecular weight of the vinyl polymer (B) is 1 million or less, preferably 30,000 to 900,000,
If it exceeds 1 million, fish eyes will occur when the resulting composition is molded, which is not preferable. Adjustment of the weight average molecular weight can be easily achieved by adjusting the amount of chain transfer agent or polymerization initiator. Here, the weight average molecular weight is a value determined in terms of polystyrene using, for example, a high performance liquid chromatograph HLC-802A manufactured by Tosoh Corporation (carrier liquid = tetrahydrofuran).
【0020】本発明の粉体組成物中におけるビニル系重
合体(B)の配合量は、(A)成分100重量部に対し
、0.1〜10重量部、好ましくは0.5〜5重量部、
さらに好ましくは0.5〜3重量部である。0.1重量
部未満では、充分な粉体特性が得られず、一方10重量
部を超えると、耐衝撃性を低下させるので好ましくない
。The blending amount of the vinyl polymer (B) in the powder composition of the present invention is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of component (A). Department,
More preferably, it is 0.5 to 3 parts by weight. If it is less than 0.1 part by weight, sufficient powder properties cannot be obtained, while if it exceeds 10 parts by weight, impact resistance is undesirably reduced.
【0021】次に、本発明の粉体組成物に用いられる滑
剤(C)の種類は特に限定されるものではないが、AB
S樹脂、MBS樹脂などに併用される常用のものでよく
、例えばステアリン酸、パルミチン酸などの高級脂肪酸
およびそのエステル類、ステアリルアルコール、パルミ
チルアルコールなどの高級アルコール類、グリセリンモ
ノステアレート、グリセリンモノオレエートなどの脂肪
酸エステル類、シリコーンオイルなどが挙げられる。
また、この滑剤(C)としては、一般に滑剤と称される
もの以外に、可塑剤、抗酸化剤、帯電防止剤なども適宜
添加することができる。これらの滑剤は、単独であるい
は2種以上を混合して用いてもよい。Next, the type of lubricant (C) used in the powder composition of the present invention is not particularly limited, but AB
Those commonly used in combination with S resin, MBS resin, etc. may be used, such as higher fatty acids and their esters such as stearic acid and palmitic acid, higher alcohols such as stearyl alcohol and palmityl alcohol, glycerin monostearate, and glycerin monostearate. Examples include fatty acid esters such as oleate, silicone oil, and the like. Moreover, as the lubricant (C), in addition to what is generally called a lubricant, a plasticizer, an antioxidant, an antistatic agent, etc. can also be appropriately added. These lubricants may be used alone or in combination of two or more.
【0022】滑剤(C)の配合量は、グラフト共重合体
(A)100重量部に対し、0〜10重量部、好ましく
は0.1〜5重量部、さらに好ましくは0.2〜5重量
部であり、10重量部を超えると耐衝撃性の低下の原因
となるので好ましくない。このように、本発明の粉体組
成物は、グラフト共重合体(A)の粉体100重量部に
特定範囲のガラス転移温度および重量平均分子量を有す
るビニル系重合体(B)、必要に応じてさらに滑剤(C
)が配合されているので、粉体特性が大幅に改良される
。The blending amount of the lubricant (C) is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the graft copolymer (A). parts by weight, and if it exceeds 10 parts by weight, it is not preferable because it causes a decrease in impact resistance. As described above, the powder composition of the present invention includes 100 parts by weight of the graft copolymer (A), a vinyl polymer (B) having a glass transition temperature and a weight average molecular weight within a specific range, and optionally a vinyl polymer (B) having a glass transition temperature and a weight average molecular weight within a specific range. Furthermore, lubricant (C
), the powder properties are significantly improved.
【0023】本発明の粉体組成物の製造方法は特に限定
されないが、例えば下記(イ)〜(ハ)のいずれか1つ
、あるいはこれらを組み合わせた方法によって容易に製
造することができる。
(イ)グラフト共重合体(A)100重量部(固形分換
算)のラテックスを凝固して得られるスラリーに、ビニ
ル系重合体(B)0.1〜10重量部(固形分換算)の
ラテックス、および滑剤(C)0〜10重量部を添加・
混合したのち、脱水、乾燥工程を経て粉体組成物を得る
方法。The method for producing the powder composition of the present invention is not particularly limited, but it can be easily produced, for example, by any one of the following methods (a) to (c), or a combination of these methods. (B) Graft copolymer (A) 0.1 to 10 parts by weight (in terms of solid content) of latex is added to a slurry obtained by coagulating 100 parts by weight (in terms of solid content) of latex of vinyl polymer (B). , and 0 to 10 parts by weight of lubricant (C) are added.
After mixing, a powder composition is obtained through dehydration and drying steps.
【0024】(ロ)グラフト共重合体(A)100重量
部(固形分換算)のラテックスを凝固して得られるスラ
リーに、ビニル系重合体(B)0.1〜10重量部(固
形分換算)のラテックスを凝固し得られるスラリーおよ
び/または該スラリーの乾燥後の粉体、ならびに滑剤(
C)0〜10重量部を添加・混合したのち、脱水、乾燥
工程を経て粉体組成物を得る方法。
(ハ)グラフト共重合体(A)の粉体100重量部に、
ビニル系重合体(B)の粉体0.1〜10重量部、およ
び滑剤(C)0〜10重量部を添加・混合し、粉体組成
物を得る方法。
前記の粉体組成物の製造方法のうち、好ましい方法は、
(イ)および/または(ロ)である。この方法によれば
、粉体特性が一段と優れた組成物が得られる。(b) Graft copolymer (A) 0.1 to 10 parts by weight (in terms of solid content) of vinyl polymer (B) is added to the slurry obtained by coagulating 100 parts by weight (in terms of solid content) of latex. A slurry obtained by coagulating the latex of ) and/or a powder after drying the slurry, and a lubricant (
C) A method of obtaining a powder composition by adding and mixing 0 to 10 parts by weight, followed by dehydration and drying steps. (c) 100 parts by weight of the powder of the graft copolymer (A),
A method of obtaining a powder composition by adding and mixing 0.1 to 10 parts by weight of a vinyl polymer (B) powder and 0 to 10 parts by weight of a lubricant (C). Among the methods for producing the powder composition described above, a preferred method is:
(a) and/or (b). According to this method, a composition with even better powder properties can be obtained.
【0025】なお、前記製造方法において、グラフト共
重合体(A)のラテックスおよびビニル系重合体(B)
のラテックスを凝固する際の凝固剤としては、硫酸、塩
酸、リン酸、硝酸などの無機酸類、酢酸などの有機酸、
あるいはナトリウム、カリウムなどのいわゆるアルカリ
金属のハロゲン化物、無機酸とのアルカリ金属塩、有機
酸とのアルカリ金属塩などが用いられる。これらの凝固
剤は、単独であるいは2種以上併用して用いられる。こ
れらの凝固剤は水溶液として用い、その添加量は特に限
定されるものではないが、ラテックスを充分に凝固させ
る量が使用される。[0025] In the above manufacturing method, the latex of the graft copolymer (A) and the vinyl polymer (B)
Coagulants for coagulating latex include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, organic acids such as acetic acid,
Alternatively, halides of so-called alkali metals such as sodium and potassium, alkali metal salts with inorganic acids, alkali metal salts with organic acids, etc. are used. These coagulants may be used alone or in combination of two or more. These coagulants are used in the form of an aqueous solution, and the amount added is not particularly limited, but is used in an amount that sufficiently coagulates the latex.
【0026】また、本発明の粉体組成物において、グラ
フト共重合体(A)の粉体の平均粒子径は、通常、30
〜1,000μm、好ましくは50〜800μm、さら
に好ましくは100〜600μm、特に好ましくは15
0〜400μmであり、一方ビニル系重合体(B)の粉
体の平均粒子径は、通常、10〜300μm、好ましく
は15〜200μm、さらに好ましくは20〜150μ
m、特に好ましくは20〜100μmである。さらに、
(A)/(B)の平均粒子径の比は、好ましくは3〜3
0、さらに好ましくは4.5〜25、特に好ましくは5
〜20である。平均粒子径が上記の範囲にあると、一段
と優れた粉体特性を有する粉体組成物が得られる。ここ
で、平均粒子径の測定は、セイシン企業(株)製、ロボ
ットシフターRPS−85を用い、粉体20gを5分間
振とうさせて分球し、その平均粒子径を標準ふるいによ
り求めた値である。Further, in the powder composition of the present invention, the average particle diameter of the powder of the graft copolymer (A) is usually 30
~1,000 μm, preferably 50 to 800 μm, more preferably 100 to 600 μm, particularly preferably 15
0 to 400 μm, while the average particle diameter of the vinyl polymer (B) powder is usually 10 to 300 μm, preferably 15 to 200 μm, and more preferably 20 to 150 μm.
m, particularly preferably 20 to 100 μm. moreover,
The average particle diameter ratio of (A)/(B) is preferably 3 to 3.
0, more preferably 4.5 to 25, particularly preferably 5
~20. When the average particle diameter is within the above range, a powder composition having even better powder properties can be obtained. Here, the average particle diameter was measured using a robot shifter RPS-85 manufactured by Seishin Enterprise Co., Ltd., by shaking 20 g of powder for 5 minutes and dividing it into spheres, and the average particle diameter was determined using a standard sieve. It is.
【0027】本発明の粉体組成物は、射出成形、押し出
し成形、真空成形、異形成形、発泡成形などによって自
動車部品、電気用部品、家庭用品、各種工業用品などの
成形することができる。その際、通常の添加剤、例えば
酸化防止剤、紫外線吸収剤、難燃剤、帯電防止剤、発泡
剤、ガラス繊維、その他の重合体、例えばポリアミド、
ポリカーボネート、熱可塑性ポリエステル、ポリフェニ
レンエーテル、ポリフッ化ビニリデン樹脂、ジエン系ゴ
ム、エチレン−プロピレン系ゴム、アクリル系ゴムなど
を配合することができる。The powder composition of the present invention can be molded into automobile parts, electrical parts, household goods, various industrial goods, etc. by injection molding, extrusion molding, vacuum forming, irregular molding, foam molding, and the like. In this case, the usual additives such as antioxidants, UV absorbers, flame retardants, antistatic agents, blowing agents, glass fibers, other polymers such as polyamides,
Polycarbonate, thermoplastic polyester, polyphenylene ether, polyvinylidene fluoride resin, diene rubber, ethylene-propylene rubber, acrylic rubber, etc. can be blended.
【0028】[0028]
【実施例】以下、本発明を実施例を挙げてさらに具体的
に説明するが、本発明はその要旨を越えない限り、以下
の実施例に何ら制約されるものではない。なお、実施例
中、部および%は特に断らないかぎり重量基準である。
また、実施例中の各種の測定は、下記の方法に拠った。EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way as long as the gist thereof is not exceeded. In the examples, parts and percentages are based on weight unless otherwise specified. Moreover, various measurements in the examples were based on the following methods.
【0029】かさ比重の測定
かさ比重(単位=g/ml)は、JIS K6721
に基づいて測定した。
流動指数の測定
「ケミカル・エンジニアリング」(Chemical
Engineering)、1965年1月18日発
行、163〜168頁に記載の方法により、安息角、圧
縮度、スパチェラ角および均一度(または凝集度)の4
つの測定値を、得られた粉体組成物について求め、それ
らの値より積算表に従って点数をつけ、これらの点数の
和で表される指数によって評価した。測定値の大きいも
のほど、流動性がよいことを示す。Measurement of bulk specific gravity Bulk specific gravity (unit = g/ml) is determined according to JIS K6721.
Measured based on. Measurement of flow index "Chemical Engineering"
Engineering), January 18, 1965, pages 163-168, the angle of repose, degree of compaction, Spatella angle, and degree of uniformity (or degree of cohesion)
Two measured values were obtained for the obtained powder composition, and scores were assigned based on these values according to an integration table, and evaluation was made using an index represented by the sum of these scores. The larger the measured value, the better the fluidity.
【0030】ラテックスの平均粒子径
太陽電子(株)製、レーザー粒径解析装置LPA−30
00/3100にて測定した。
崩壊率の測定
得られた粉体組成物25gに、一定の荷重(3kg/c
m2 )を30分かけてブロック(形状;円柱状、寸法
;4cm×2cm)を製造し、このブロックに一定の振
動(振動数;60Hz)を200秒間与えて崩壊させ、
崩壊された粉体のうち、16メッシュパスの粉体の重量
を、元のブロックの全重量に対する百分率で表した。そ
の百分率の数値を崩壊率といい、数値の大きいものほど
ブロッキングし難いことを示す。なお、崩壊率は、粉体
組成物乾燥直後、乾燥ののち10時間放置したものにつ
いて、それぞれ測定した。また、乾燥直後の粉体組成物
について、荷重負荷時間を1カ月間かけて作製したブロ
ックについても、同様にして崩壊率を測定した。
アイゾット衝撃強度
平均重合度が700である塩化ビニル樹脂100部と、
グラフト共重合体粉体あるいはその組成物15部、ジブ
チルスズマレート系安定剤2部、フタル酸ジオクチル3
部およびモンタン酸ブチレングリコールエステル0.5
部との混合物を、ヘンシェル型ミキサー内に仕込み、1
20℃まで昇温攪拌したのち、50℃まで冷却し、これ
を165℃ロールで7分間混練りし、次いで180℃で
1/2インチ×1/4インチ×2.5インチの試験片に
プレス成形した。この試験片10本を用いて、測定温度
23℃、ASTM D256に準じてアイゾット衝撃
強度を測定した。単位は、kg・cm/cmである。
フィッシュアイ数
平均重合度が700である塩化ビニル樹脂100部と、
グラフト共重合体粉体あるいはその組成物15部、ジブ
チルスズマレート系安定剤2部、フタル酸ジオクチル3
部およびモンタン酸ブチレングリコールエステル0.5
部との混合物を、ヘンシェル型ミキサー内に仕込み、1
20℃まで昇温攪拌したのち、50℃まで冷却し、これ
を押し出し機を用いて厚さ0.2mmのT−ダイシート
を作製し、50×1,000mm中のフィッシュアイ数
を測定した。20枚中に認められたフィッシアイ数を平
均した。Average particle size of latex Laser particle size analyzer LPA-30 manufactured by Taiyodenshi Co., Ltd.
Measured at 00/3100. Measurement of disintegration rate A constant load (3 kg/c) was applied to 25 g of the obtained powder composition.
m2) for 30 minutes to produce a block (shape: cylindrical, dimensions: 4 cm x 2 cm), and this block was given constant vibration (frequency: 60 Hz) for 200 seconds to collapse.
Among the disintegrated powders, the weight of the powder of 16 mesh passes was expressed as a percentage of the total weight of the original block. The percentage value is called the decay rate, and the larger the value, the more difficult it is to block. Note that the disintegration rate was measured immediately after drying the powder composition and after drying for 10 hours. In addition, the disintegration rate was similarly measured for a block prepared by applying a load for one month using the powder composition immediately after drying. 100 parts of a vinyl chloride resin having an Izod impact strength average degree of polymerization of 700;
15 parts of graft copolymer powder or its composition, 2 parts of dibutyltin malate stabilizer, 3 parts of dioctyl phthalate
part and montanic acid butylene glycol ester 0.5
Place the mixture with 1 part into a Henschel type mixer, and
The temperature was raised to 20°C and stirred, then cooled to 50°C, kneaded with a 165°C roll for 7 minutes, and then pressed at 180°C into a 1/2 inch x 1/4 inch x 2.5 inch test piece. Molded. Using these 10 test pieces, Izod impact strength was measured at a measurement temperature of 23° C. according to ASTM D256. The unit is kg·cm/cm. 100 parts of a vinyl chloride resin having a fisheye number average degree of polymerization of 700;
15 parts of graft copolymer powder or its composition, 2 parts of dibutyltin malate stabilizer, 3 parts of dioctyl phthalate
part and montanic acid butylene glycol ester 0.5
Place the mixture with 1 part into a Henschel type mixer, and
After the temperature was raised to 20° C. and stirred, it was cooled to 50° C., and a T-die sheet with a thickness of 0.2 mm was produced using an extruder, and the number of fish eyes in 50×1,000 mm was measured. The number of fisheyes observed in the 20 sheets was averaged.
【0031】実施例1
グラフト共重合体(A)のラテックスの製造脱イオン水
150部、1,3−ブタジエン66部、スチレン34部
、ラウリル酸カリウム2.0部、リン酸カリウム0.6
部、ジイソプロピルベンゼンハイドロパーオキサイド0
.06部、および硫酸第一鉄0.01部、エチレンジア
ミンテトラ酢酸二ナトリウム0.025部、ホルムアル
デヒドスルホキシル酸ナトリウム0.04部の混合物を
、チッ素置換したオートクレーブ中に仕込み、攪拌しな
がら5℃で6時間重合し、重合転化率90%で乳化重合
を集結させた。次いで、得られたゴム質重合体ラテック
ス中に、水蒸気を吹き込み、未反応単量体を除去した。Example 1 Preparation of latex of graft copolymer (A) 150 parts of deionized water, 66 parts of 1,3-butadiene, 34 parts of styrene, 2.0 parts of potassium laurate, 0.6 parts of potassium phosphate.
parts, diisopropylbenzene hydroperoxide 0
.. A mixture of 0.06 parts of ferrous sulfate, 0.01 part of ferrous sulfate, 0.025 parts of disodium ethylenediaminetetraacetate, and 0.04 parts of sodium formaldehyde sulfoxylate was placed in a nitrogen-substituted autoclave, and heated at 5°C with stirring. Polymerization was carried out for 6 hours, and emulsion polymerization was concentrated at a polymerization conversion rate of 90%. Next, water vapor was blown into the obtained rubbery polymer latex to remove unreacted monomers.
【0032】次いで、チッ素置換したフラスコ中に、前
記のようにして製造したゴム質重合体ラテックスを固形
分換算で60部、脱イオン水150部(ゴム質重合体ラ
テックス中の水分を含む)を仕込み、昇温し、内温が7
0℃に達した時点で、クメンハイドロパーオキサイド0
.2部、スチレン14部およびメチルメタクリレート2
6部との混合物と、ホルムアルデヒドスルホキシル酸ナ
トリウム0.10部を脱イオン水20部に溶解した溶液
とを、別々の供給口より同時に4時間かけて連続滴下し
、さらに1時間攪拌を続けてグラフト重合を完結させた
。得られたグラフト共重合体ラテックスをA−1とした
。ラテックスA−1の平均粒子径は、1,500Åであ
った。Next, in a nitrogen-substituted flask, 60 parts of the rubbery polymer latex produced as described above in terms of solid content and 150 parts of deionized water (including water in the rubbery polymer latex) were added. Prepare and raise the temperature until the internal temperature is 7.
When the temperature reaches 0℃, cumene hydroperoxide is 0.
.. 2 parts, 14 parts of styrene and 2 parts of methyl methacrylate
A mixture of 6 parts of sodium formaldehyde sulfoxylate and a solution of 0.10 parts of sodium formaldehyde sulfoxylate dissolved in 20 parts of deionized water were simultaneously added dropwise from separate feed ports over a period of 4 hours, and stirring was continued for an additional hour. Graft polymerization was completed. The obtained graft copolymer latex was designated as A-1. The average particle diameter of latex A-1 was 1,500 Å.
【0033】ビニル系重合体(B)のラテックスの製造
脱イオン水180部、ラウリル酸カリウム2部、メチル
メタクリレート100部、ジイソプロピルベンゼンハイ
ドロパーオキサイド0.12部、硫酸第一鉄0.02部
、エチレンジアミンテトラ酢酸二ナトリウム0.05部
、ホルムアルデヒドスルホキシル酸ナトリウム0.08
部の混合水溶液を、チッ素置換したオートクレーブに仕
込み、攪拌しながら60℃で2時間重合し、重合転化率
100%で重合を完結させ、ビニル系重合体ラテックス
B−1を得た。このビニル系重合体ラテックスB−1の
平均粒子径は700Å、また該ラテックスを構成する重
合体のガラス転移温度は100℃、重量平均分子量は8
0万であった。Production of latex of vinyl polymer (B) 180 parts of deionized water, 2 parts of potassium laurate, 100 parts of methyl methacrylate, 0.12 parts of diisopropylbenzene hydroperoxide, 0.02 parts of ferrous sulfate, Disodium ethylenediaminetetraacetate 0.05 part, sodium formaldehyde sulfoxylate 0.08
A mixed aqueous solution of 1 part was charged into a nitrogen-substituted autoclave, and polymerized with stirring at 60°C for 2 hours to complete the polymerization at a polymerization conversion rate of 100% to obtain vinyl polymer latex B-1. The average particle diameter of this vinyl polymer latex B-1 is 700 Å, the glass transition temperature of the polymer constituting the latex is 100°C, and the weight average molecular weight is 8
It was 0,000.
【0034】粉体組成物の製造
前記で得られたグラフト共重合体(A)のラテックスA
−1を固形分換算で100部に対し、老化防止剤として
ブチル化ヒドロキシトルエン1部を添加したのち、40
℃の0.5%硫酸水溶液で凝固を行った。得られたスラ
リーを90℃まで昇温し、5分間保持し、次いで前記で
得られたビニル系重合体(B)のラテックスB−1を固
形分換算で3部、および滑剤としてグリセリンモノステ
アレート1部を添加し、さらに混合しながら5分間保持
した。その後、脱水、乾燥し、粉体組成物を得た。粉体
組成物中のA−1の粒子の平均粒子径は、約240μm
であった。結果を表1に示す。Production of powder composition Latex A of the graft copolymer (A) obtained above
After adding 1 part of butylated hydroxytoluene as an anti-aging agent to 100 parts of -1 in terms of solid content, 40 parts of
Coagulation was performed with a 0.5% aqueous sulfuric acid solution at °C. The temperature of the obtained slurry was raised to 90°C and held for 5 minutes, and then 3 parts of latex B-1 of the vinyl polymer (B) obtained above was added in terms of solid content, and glycerin monostearate was added as a lubricant. 1 part was added and held for 5 minutes with further mixing. Thereafter, it was dehydrated and dried to obtain a powder composition. The average particle diameter of the particles of A-1 in the powder composition is approximately 240 μm
Met. The results are shown in Table 1.
【0035】実施例2〜5
ビニル系重合体(B)のラテックスB−1の量、あるい
は滑剤(C)であるグリセリンモノステアレートの量を
表1に示すように変更した以外は、実施例1と同様にし
て粉体組成物を得た。粉体組成物中のA−1の平均粒子
径は、約240μmであった。結果を表1に示す。Examples 2 to 5 Examples 2 to 5 except that the amount of latex B-1 of the vinyl polymer (B) or the amount of glycerin monostearate as the lubricant (C) was changed as shown in Table 1. A powder composition was obtained in the same manner as in Example 1. The average particle size of A-1 in the powder composition was about 240 μm. The results are shown in Table 1.
【0036】実施例6
実施例1で用いたラテックスA−1、ラテックスB−1
のそれぞれを、40℃の0.5%硫酸水溶液で凝固させ
、90℃で5分間保持して、各スラリーを得た。次いで
、ラテックスA−1から得たスラリーを固形分換算で1
00部、ラテックスB−1から得たスラリーを固形分換
算で3部、および滑剤であるグリセリンモノステアレー
ト1部を混合し、その後、脱水、乾燥し、粉体組成物を
得た。結果を表2に示す。Example 6 Latex A-1 and Latex B-1 used in Example 1
Each of these was coagulated with a 0.5% sulfuric acid aqueous solution at 40°C and held at 90°C for 5 minutes to obtain each slurry. Next, the slurry obtained from latex A-1 was reduced to 1 in terms of solid content.
00 parts, 3 parts in terms of solid content of the slurry obtained from Latex B-1, and 1 part of glycerin monostearate as a lubricant were mixed, followed by dehydration and drying to obtain a powder composition. The results are shown in Table 2.
【0037】実施例7
実施例6で作製したラテックスA−1から得たスラリー
を固形分換算で100部に、実施例6で作製したラテッ
クスB−1から得たスラリーを脱水、乾燥して得た粉体
3部、およびグリセリンモノステアレート1部を混合、
その後、脱水、乾燥して粉体組成物を得た。結果を表2
に示す。Example 7 The slurry obtained from latex A-1 prepared in Example 6 was reduced to 100 parts in terms of solid content, and the slurry obtained from latex B-1 prepared in Example 6 was dehydrated and dried. Mix 3 parts of powder and 1 part of glycerin monostearate,
Thereafter, it was dehydrated and dried to obtain a powder composition. Table 2 shows the results.
Shown below.
【0038】実施例8
実施例1のラテックスB−1の重合処方において、メチ
ルメタクリレート100部を、メチルメタクリレート9
5部およびブチルアクリレート5部とし、分子量調節剤
としてt−ドデシルメルカプタン0.5部を用いる以外
は、実施例1と同様の重合処方によりビニル系重合体(
B)のラテックスB−2を得た。このラテックスB−2
の平均粒子径は650Å、また該ラテックスを構成する
重合体のガラス転移温度は87℃、重量平均分子量は4
0万であった。このビニル系重合体ラテックスB−2を
用いる以外は、実施例1と同様にして粉体組成物を得た
。結果を表2に示す。Example 8 In the polymerization recipe of latex B-1 in Example 1, 100 parts of methyl methacrylate was replaced with 9 parts of methyl methacrylate.
A vinyl polymer (
Latex B-2 of B) was obtained. This latex B-2
The average particle diameter of the latex is 650 Å, the glass transition temperature of the polymer constituting the latex is 87°C, and the weight average molecular weight is 4.
It was 0,000. A powder composition was obtained in the same manner as in Example 1 except for using this vinyl polymer latex B-2. The results are shown in Table 2.
【0039】実施例9
滑剤(C)であるグリセリンモノステアレートをエポキ
シ化大豆油に変更した以外は、実施例1と同様にして粉
体組成物を得た。結果を表2に示す。
実施例10
滑剤(C)として、グリセリンモノステアレート0.5
部およびエポキシ化大豆油0.5部を用いる以外は、実
施例1と同様にして粉体組成物を得た。結果を表3に示
す。
実施例11
滑剤(C)を用いない以外は、実施例1と同様にして粉
体組成物を得た。結果を表3に示す。
実施例12
ラテックスA−1を、実施例1と同様に凝固、脱水、乾
燥して得た粉体と、ラテックスBBA1を同様に凝固、
脱水、乾燥して得た粉体とを、表2に示す処方で混合し
て粉体組成物を得た。結果を表3に示す。Example 9 A powder composition was obtained in the same manner as in Example 1, except that the lubricant (C), glycerin monostearate, was changed to epoxidized soybean oil. The results are shown in Table 2. Example 10 Glycerin monostearate 0.5 as lubricant (C)
A powder composition was obtained in the same manner as in Example 1, except that 0.5 parts of epoxidized soybean oil and 0.5 parts of epoxidized soybean oil were used. The results are shown in Table 3. Example 11 A powder composition was obtained in the same manner as in Example 1 except that the lubricant (C) was not used. The results are shown in Table 3. Example 12 A powder obtained by coagulating, dehydrating, and drying latex A-1 in the same manner as in Example 1, and a powder obtained by coagulating latex BBA1 in the same manner as in Example 1.
The powder obtained by dehydration and drying was mixed with the formulation shown in Table 2 to obtain a powder composition. The results are shown in Table 3.
【0040】比較例1〜3
ラテックスB−1の量を本発明の上限を超えて使用する
か(比較例1)、用いないか(比較例2)、あるいは滑
剤(C)の量を本発明の上限を超えて使用する(比較例
3)以外は、いずれも実施例1と同様にして粉体組成物
を得た。結果を表4に示す。Comparative Examples 1 to 3 The amount of latex B-1 is used in an amount exceeding the upper limit of the present invention (Comparative Example 1) or not (Comparative Example 2), or the amount of lubricant (C) is Powder compositions were obtained in the same manner as in Example 1, except that the upper limit was used (Comparative Example 3). The results are shown in Table 4.
【0041】比較例4
実施例1のグラフト共重合体(A)のラテックスA−1
の重合処方において、ゴム質重合体ラテックスを固形分
換算で20部、スチレン28部、メチルメタクリレート
52部を用いた以外は、実施例1と同様にしてグラフト
共重合体ラテックスA−2を得た。このラテックスA−
2の平均粒子径は、1,450Åであった。グラフト共
重合体ラテックスA−1に代えて、このグラフト共重合
体ラテックスA−2用いる以外は、実施例1と同様にし
て粉体組成物を得た。結果を表5に示す。Comparative Example 4 Latex A-1 of the graft copolymer (A) of Example 1
Graft copolymer latex A-2 was obtained in the same manner as in Example 1, except that in the polymerization recipe, 20 parts of rubbery polymer latex, 28 parts of styrene, and 52 parts of methyl methacrylate were used in terms of solid content. . This latex A-
The average particle diameter of No. 2 was 1,450 Å. A powder composition was obtained in the same manner as in Example 1, except that this graft copolymer latex A-2 was used instead of graft copolymer latex A-1. The results are shown in Table 5.
【0042】比較例5
実施例1のグラフト共重合体(A)のラテックスA−1
の重合処方において、ゴム質重合体ラテックスを固形分
換算で90部、スチレン3.5部、メチルメタクリレー
ト6.5部を用いた以外は、実施例1と同様にしてグラ
フト共重合体ラテックスA−3を得た。このラテックス
A−3の平均粒子径は、1,500Åであった。グラフ
ト共重合体ラテックスA−1に代えて、このグラフト共
重合体ラテックスA−3用いる以外は、実施例1と同様
にして粉体組成物を得た。結果を表5に示す。Comparative Example 5 Latex A-1 of the graft copolymer (A) of Example 1
Graft copolymer latex A- I got 3. The average particle diameter of this latex A-3 was 1,500 Å. A powder composition was obtained in the same manner as in Example 1, except that this graft copolymer latex A-3 was used instead of graft copolymer latex A-1. The results are shown in Table 5.
【0043】比較例6
実施例1のラテックスB−1の重合処方において、ジイ
ソプロピルベンゼンハイドロパーオキサイド0.06部
、硫酸第一鉄0.01部、エチレンジアミンテトラ酢酸
二ナトリウム0.025部、ホルムアルデヒドスルホキ
シル酸ナトリウム0.04部の混合物を使用し、重合温
度を40℃にして3時間重合を行う以外は、実施例1と
同様の重合処方によりビニル系重合体(B)のラテック
スB−3を得た。このラテックスB−3の平均粒子径は
720Å、また該ラテックスを構成する重合体のガラス
転移温度は100℃、重量平均分子量は150万であっ
た。このビニル系重合体ラテックスB−3を用いる以外
は、実施例1と同様にして粉体組成物を得た。結果を表
5に示す。Comparative Example 6 In the polymerization recipe of Latex B-1 of Example 1, 0.06 part of diisopropylbenzene hydroperoxide, 0.01 part of ferrous sulfate, 0.025 part of disodium ethylenediaminetetraacetate, and formaldehyde sulfonate were added. Latex B-3 of vinyl polymer (B) was prepared using the same polymerization recipe as in Example 1, except that a mixture of 0.04 parts of sodium xylate was used and the polymerization temperature was 40°C for 3 hours. Obtained. The average particle diameter of this latex B-3 was 720 Å, the glass transition temperature of the polymer constituting the latex was 100° C., and the weight average molecular weight was 1.5 million. A powder composition was obtained in the same manner as in Example 1 except for using this vinyl polymer latex B-3. The results are shown in Table 5.
【0044】比較例7
実施例1のラテックスB−1の重合処方において、メチ
ルメタクリレート100部を、メチルメタクリレート3
0部とブチルアクリレート70部に代えた以外は、実施
例1と同様の重合処方によりビニル系重合体(B)のラ
テックスB−4を得た。このラテックスB−4の平均粒
子径は700Å、また該ラテックスを構成する重合体の
ガラス転移温度は31℃、重量平均分子量は75万であ
った。このビニル系重合体ラテックスB−4を用いる以
外は、実施例1と同様にして粉体組成物を得た。結果を
表5に示す。なお、比較例1〜7の粉体組成物において
、(A)成分の粉体平均粒子径は、約240μmであっ
た。Comparative Example 7 In the polymerization recipe of latex B-1 of Example 1, 100 parts of methyl methacrylate was replaced with 3 parts of methyl methacrylate.
Latex B-4 of vinyl polymer (B) was obtained using the same polymerization recipe as in Example 1, except that 0 parts and 70 parts of butyl acrylate were used. The average particle diameter of this latex B-4 was 700 Å, the glass transition temperature of the polymer constituting the latex was 31° C., and the weight average molecular weight was 750,000. A powder composition was obtained in the same manner as in Example 1 except for using this vinyl polymer latex B-4. The results are shown in Table 5. In addition, in the powder compositions of Comparative Examples 1 to 7, the powder average particle diameter of component (A) was about 240 μm.
【0045】表1〜3から明らかなように、実施例1〜
11は、本発明の粉体組成物であり、本発明の目的とす
る粉体組成物が得られている。これに対し、表4から明
らかなように、比較例1は、ビニル系重合体(B)の使
用量が本発明の範囲を超えた例であり、耐衝撃性に劣る
。比較例2は、ビニル系重合体(B)を用いない例であ
り、粉体特性が改良されていない。が劣る。As is clear from Tables 1 to 3, Examples 1 to 3
No. 11 is the powder composition of the present invention, and the powder composition targeted by the present invention has been obtained. On the other hand, as is clear from Table 4, Comparative Example 1 is an example in which the amount of vinyl polymer (B) used exceeds the range of the present invention, and the impact resistance is poor. Comparative Example 2 is an example in which the vinyl polymer (B) was not used, and the powder properties were not improved. is inferior.
【0046】また表4から明らかなように、比較例4は
、グラフト共重合体(A)中のゴム質重合体の含有率が
本発明の範囲未満の例であり、本発明の粉体組成物によ
らなくても粉体特性が優れたものが得られることが分か
る。比較例5は、グラフト共重合体(A)中のゴム質重
合体の含有率が本発明の範囲を超えた例であり、粉体特
性の改良された粉体組成物が得られない。比較例6は、
ビニル系重合体(B)の重量平均分子量が本発明の範囲
を超えた例であり、フィッシュアイが多くなる。比較例
7は、ビニル系重合体(B)のガラス転移温度が本発明
の範囲未満の例であり、粉体特性が劣る。Furthermore, as is clear from Table 4, Comparative Example 4 is an example in which the content of the rubbery polymer in the graft copolymer (A) is below the range of the present invention, and the powder composition of the present invention is It can be seen that powder with excellent properties can be obtained regardless of the material used. Comparative Example 5 is an example in which the content of the rubbery polymer in the graft copolymer (A) exceeds the range of the present invention, and a powder composition with improved powder properties cannot be obtained. Comparative example 6 is
This is an example in which the weight average molecular weight of the vinyl polymer (B) exceeds the range of the present invention, resulting in increased fish eyes. Comparative Example 7 is an example in which the glass transition temperature of the vinyl polymer (B) is lower than the range of the present invention, and the powder properties are poor.
【0047】[0047]
【表1】[Table 1]
【0048】[0048]
【表2】[Table 2]
【0049】[0049]
【表3】[Table 3]
【0050】[0050]
【表4】[Table 4]
【0051】[0051]
【表5】[Table 5]
【0052】[0052]
【発明の効果】本発明の粉体組成物は、ブロッキング現
象、ブリッジング現象、輸送ライン中の詰まり現象など
がなく、その結果粉体計量の自動化、輸送方式の大型化
などの省力化が可能である。[Effects of the Invention] The powder composition of the present invention does not cause blocking phenomena, bridging phenomena, clogging phenomena in transportation lines, etc., and as a result, it is possible to automate powder weighing and save labor by increasing the size of transportation methods. It is.
Claims (2)
量%であるグラフト共重合体(A)の粉体100重量部
に対し、ガラス転移温度が70〜170℃でかつ重量平
均分子量が100万以下のビニル系重合体(B)の粉体
0.1〜10重量部、および滑剤(C)0〜10重量部
を主成分とする粉体組成物。Claim 1: For 100 parts by weight of a powder of graft copolymer (A) having a rubbery polymer content of 30 to 80% by weight, a powder having a glass transition temperature of 70 to 170°C and a weight average molecular weight of A powder composition whose main components are 0.1 to 10 parts by weight of a vinyl polymer (B) having a weight of 1 million or less, and 0 to 10 parts by weight of a lubricant (C).
の方法による請求項1記載の粉体組成物の製造方法。 (イ)グラフト共重合体(A)100重量部(固形分換
算)のラテックスを凝固して得られるスラリーに、ビニ
ル系重合体(B)0.1〜10重量部(固形分換算)の
ラテックス、および滑剤(C)0〜10重量部を添加・
混合したのち、脱水、乾燥工程を経て粉体組成物を得る
方法。 (ロ)グラフト共重合体(A)100重量部(固形分換
算)のラテックスを凝固して得られるスラリーに、ビニ
ル系重合体(B)0.1〜10重量部(固形分換算)の
ラテックスを凝固し得られるスラリーおよび/または該
スラリーの乾燥後の粉体、ならびに滑剤(C)0〜10
重量部を添加・混合したのち、脱水、乾燥工程を経て粉
体組成物を得る方法。 (ハ)グラフト共重合体(A)の粉体100重量部に、
ビニル系重合体(B)の粉体0.1〜10重量部、およ
び滑剤(C)0〜10重量部を添加・混合し、粉体組成
物を得る方法。2. A method for producing the powder composition according to claim 1, using at least one of the following methods (a) to (c). (B) Graft copolymer (A) 0.1 to 10 parts by weight (in terms of solid content) of latex is added to a slurry obtained by coagulating 100 parts by weight (in terms of solid content) of latex of vinyl polymer (B). , and 0 to 10 parts by weight of lubricant (C) are added.
After mixing, a powder composition is obtained through dehydration and drying steps. (B) Graft copolymer (A) 100 parts by weight (in terms of solid content) of latex is coagulated into a slurry obtained, and vinyl polymer (B) 0.1 to 10 parts by weight (in terms of solid content) of latex is added to the slurry. A slurry obtained by coagulating and/or a powder after drying the slurry, and a lubricant (C) 0 to 10
After adding and mixing parts by weight, a powder composition is obtained through dehydration and drying steps. (c) 100 parts by weight of the powder of the graft copolymer (A),
A method of obtaining a powder composition by adding and mixing 0.1 to 10 parts by weight of a vinyl polymer (B) powder and 0 to 10 parts by weight of a lubricant (C).
Priority Applications (1)
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JP13332991A JP3132040B2 (en) | 1991-05-10 | 1991-05-10 | Powder composition and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13332991A JP3132040B2 (en) | 1991-05-10 | 1991-05-10 | Powder composition and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04335052A true JPH04335052A (en) | 1992-11-24 |
JP3132040B2 JP3132040B2 (en) | 2001-02-05 |
Family
ID=15102172
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Application Number | Title | Priority Date | Filing Date |
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JP13332991A Expired - Fee Related JP3132040B2 (en) | 1991-05-10 | 1991-05-10 | Powder composition and method for producing the same |
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JP (1) | JP3132040B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005017026A1 (en) * | 2003-08-14 | 2005-02-24 | Mitsubishi Rayon Co., Ltd. | Material containing rubbery polymer, process for producing the same, and thermoplastic resin containing the same |
JP2007246616A (en) * | 2006-03-14 | 2007-09-27 | Kaneka Corp | Resin composition for powder molding and molded product |
CN113853402A (en) * | 2019-03-28 | 2021-12-28 | 株式会社钟化 | Method for producing powder and powder |
-
1991
- 1991-05-10 JP JP13332991A patent/JP3132040B2/en not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005017026A1 (en) * | 2003-08-14 | 2005-02-24 | Mitsubishi Rayon Co., Ltd. | Material containing rubbery polymer, process for producing the same, and thermoplastic resin containing the same |
JPWO2005017026A1 (en) * | 2003-08-14 | 2006-10-12 | 三菱レイヨン株式会社 | Rubber polymer-containing material, production method thereof, and thermoplastic resin blended with the same |
JP4739956B2 (en) * | 2003-08-14 | 2011-08-03 | 三菱レイヨン株式会社 | Rubber polymer-containing material, production method thereof, and thermoplastic resin containing the same |
JP2007246616A (en) * | 2006-03-14 | 2007-09-27 | Kaneka Corp | Resin composition for powder molding and molded product |
CN113853402A (en) * | 2019-03-28 | 2021-12-28 | 株式会社钟化 | Method for producing powder and powder |
Also Published As
Publication number | Publication date |
---|---|
JP3132040B2 (en) | 2001-02-05 |
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