CN104057554A - Process for production of acrylic resin pellet, and process for production of film - Google Patents
Process for production of acrylic resin pellet, and process for production of film Download PDFInfo
- Publication number
- CN104057554A CN104057554A CN201410200553.1A CN201410200553A CN104057554A CN 104057554 A CN104057554 A CN 104057554A CN 201410200553 A CN201410200553 A CN 201410200553A CN 104057554 A CN104057554 A CN 104057554A
- Authority
- CN
- China
- Prior art keywords
- acrylic resin
- particle
- film
- pellet
- temperature
- 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
- 238000000034 method Methods 0.000 title claims abstract description 172
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 119
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 119
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 80
- 239000008188 pellet Substances 0.000 title claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 166
- 238000003860 storage Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 34
- 230000005540 biological transmission Effects 0.000 claims abstract description 14
- 239000010408 film Substances 0.000 claims description 100
- 230000009477 glass transition Effects 0.000 claims description 59
- 239000012535 impurity Substances 0.000 claims description 27
- -1 polypropylene Polymers 0.000 claims description 23
- 239000008187 granular material Substances 0.000 claims description 15
- 238000012546 transfer Methods 0.000 claims description 14
- 238000004806 packaging method and process Methods 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 230000008676 import Effects 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical group O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 3
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical group O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000012458 free base Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 40
- 229920005989 resin Polymers 0.000 abstract description 40
- 238000000465 moulding Methods 0.000 abstract 3
- 239000007789 gas Substances 0.000 description 37
- 229920000642 polymer Polymers 0.000 description 30
- 230000000694 effects Effects 0.000 description 19
- 238000005520 cutting process Methods 0.000 description 18
- 238000001816 cooling Methods 0.000 description 17
- 238000005538 encapsulation Methods 0.000 description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000005266 casting Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 238000005469 granulation Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 150000002596 lactones Chemical group 0.000 description 7
- 238000000059 patterning Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009434 installation Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 210000000689 upper leg Anatomy 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- IRXDXDBTHUPFNG-UHFFFAOYSA-N 2-methylbutan-2-yl nonanoate Chemical compound CCCCCCCCC(=O)OC(C)(C)CC IRXDXDBTHUPFNG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- GNVVCXKPELIBPR-UHFFFAOYSA-N 1-methylpyrrole-2,5-dione Chemical compound CN1C(C=CC1=O)=O.CN1C(C=CC1=O)=O GNVVCXKPELIBPR-UHFFFAOYSA-N 0.000 description 1
- XBHHVVHQVJQMSL-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1.O=C1C=CC(=O)N1C1=CC=CC=C1 XBHHVVHQVJQMSL-UHFFFAOYSA-N 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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- ARQRPTNYUOLOGH-UHFFFAOYSA-N chcl3 chloroform Chemical compound ClC(Cl)Cl.ClC(Cl)Cl ARQRPTNYUOLOGH-UHFFFAOYSA-N 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- JNNKWUPPLJTSSJ-UHFFFAOYSA-N chloromethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCl JNNKWUPPLJTSSJ-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000005453 pelletization 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
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The object is to establish a production process which can produce a pellet having a low moisture content efficiently and stably even when a highly hygroscopic resin such as an acrylic resin is used. Specifically disclosed is a process for producing an acrylic resin pellet, which comprises the following steps: a molding step of molding an acrylic resin in a molten state into a pellet; and, subsequent to the molding step, a transport step of transporting the pellet into a storage silo (5), wherein the temperature of the pellet is kept at 70 DEG C or higher during the transport step. Also disclosed is an acrylic resin package body comprising an acrylic resin pellet sealed with a material having a water vapor transmission rate of less than 1.0 g/m2/24-hours, wherein the acrylic resin pellet has a moisture content of less than 300 ppm and contains a foreign matter having a diameter of 2 [mu]m or greater in an amount of less than 500 particles/g as measured on a liquid-borne particle counter.
Description
The application is dividing an application of application number: 200880100558.X, the denomination of invention application for a patent for invention that is " manufacture method of acrylic resin pellet and the manufacture method of film ", and the applying date is on August 8th, 2008.
Technical field
The manufacture method that the present invention relates to a kind of manufacture method of acrylic resin pellet and use the film of this particle.
Background technology
Resin particle is manufactured by following manner, , to utilize extrusion moulding machine to form in the resin injection template (dies plate) of molten condition, and by line thigh patterning method (strand cuttingmethod), thermal cutting method (hot cutting method), underwater cutting process (underwatercutting method), or water spray patterning method (watering cutting method) becomes grain shape by extruded resin cleavage, and by water-cooled solidification mode of contacting with water etc., till the resin of cut molten condition is cooled to below glass transition temperature (glass transitiontemperature).
The particle of manufacturing in this way can be used as through melt-processed the raw material of film (film), thin plate (sheet), various formed bodies.At this, if while offering melt-processed known, the water content of particle is higher, and while carrying out melt-shaping so, resin can decompose, or produces bubble or micropore (microvoid), crazing (silver streak) etc. and cause bad order.
If it is higher particularly to have acrylic resin water content when offering melt-processed of ring structure in main chain, can causes that resin properties declines because ring structure decomposes, or produce bubble because of decomposition gas.So, conventionally can, before melt-processed, the drying process that is used for reducing moisture contained in acrylic resin be set.
Under common environment, more than the water content of acrylic resin is generally 10,000ppm, this acrylic resin is dewatered to the water content that can not cause bad order when melt-processed, for example need at more than 100 ℃ temperature, be dried more than 5 hours.In this case, exist productivity likely to reduce or in drying process, likely sneak into the problems such as impurity.
Therefore,, in order to omit described drying process, proposed when manufacturing particle, water content to be suppressed for lower method (for example, with reference to patent documentation 1, patent documentation 2).
In patent documentation 1, having disclosed a kind of polyolefin (polyolefin) is the manufacture method of resin particle, and the method not adopts water-cooled solidification mode when cooling, but blows the attached air that is mixed with water to particle.
In addition, in patent documentation 2, disclosed a kind of method of using the transfer device of the polyester granulate that is provided with pre-dryers after granulation (pelletizing).
[patent documentation 1] Japanese patent laid-open 6-315930 communique (on November 15th, 1994 is open)
[patent documentation 2] Japan Patent Beneficial 7-26107 communique (May 16 nineteen ninety-five is open)
Summary of the invention
But, when the method for described patent documentation 1, patent documentation 2 is applied to acrylic resin, there is productive raising inadequate problem.
Particularly, the method of patent documentation 1 can not shorten drying time for the such hygroscopicity of vistanex is very high resin, but the bibulous resin moisture absorption at short notice that acrylic resin is such, and need for a long time in order to remove the moisture of temporary transient moisture absorption, so can shorten hardly drying time.
In addition, same with patent documentation 1, the method for patent documentation 2 is because be to be dried after particle moisture absorption, so if the so fast resin of rate of moisture absorption of acrylic resin can shorten so drying time hardly.
The present invention forms in view of described Study on Problems, even if the object of the invention is to realize the bibulous resins such as a kind of employing acrylic resin, also can efficiency well and stably manufacture the manufacture method of the particle that moisture content is low, and the manufacture method of using the film of this particle.
In order to solve described problem, the manufacture method of acrylic resin pellet of the present invention is characterised in that and comprises: forming process, is configured as particle by the acrylic resin of molten condition; And transfering process, after described forming process, by described transfer of granules in storage bin; And, in described transfering process, the temperature of particle is remained on more than 70 ℃.
According to described method, because the temperature of particle is remained on more than 70 ℃ in described transfering process, so can suppress the moisture absorption of particle before arriving storage bin.
Therefore,, even if given play to bibulous resins such as adopting acrylic resin, also can efficiency well and stably manufacture the effect of the particle that moisture content is low.
The manufacture method of acrylic resin pellet of the present invention preferably also comprises refrigerating work procedure, wherein, in storage bin, is removing cooling described particle under wet environment.
According to described method, can suppress moisture absorption cooling particulate, so given play to, can efficiency well and stably manufacture the further effect through the low particle of cooling moisture content.
The manufacture method of acrylic resin pellet of the present invention preferably after described forming process, before transfering process, also comprise the temperature of described particle be cooled to the operation below the glass transition temperature of described acrylic resin, and in described transfering process, the temperature of particle is remained on more than 70 ℃, in the scope below the glass transition temperature of described acrylic resin.
According to described method, because the temperature of particle in described transfering process is in the scope remaining on below the glass transition temperature of 70 ℃ of above, described acrylic resins, so given play to not only, can before arriving storage bin, suppress particle moisture absorption, but also can suppress the further effect of intergranular melting.
For the manufacture method of acrylic resin pellet of the present invention, the glass transition temperature of preferred described acrylic resin is more than 110 ℃.
According to described method, can give play to the further effect that more suppresses intergranular melting.And, at higher temperature, also can avoid intergranular melting, so can carry out transfering process at higher temperature.Result has been given play to the further effect that can manufacture the particle that moisture content is lower.
For the manufacture method of acrylic resin pellet of the present invention, in the main chain of preferred described acrylic resin, there is ring structure.
According to described method, because there is ring structure in the main chain of acrylic resin, so the glass transition temperature of acrylic resin improves.So, given play to the further effect that more suppresses intergranular melting.And, at higher temperature, also can avoid intergranular melting, so can carry out transfering process at higher temperature.Result has been given play to the further effect that can manufacture the particle that moisture content is lower.
In order to solve described problem, the manufacture method of film of the present invention is characterised in that and comprises: utilize described manufacture method of the present invention to manufacture the operation of acrylic resin pellet; And described acrylic resin pellet is configured as to the operation of film.
According to described method, because be to use the acrylic resin pellet obtaining by manufacture method of the present invention to manufacture film, so given play to following effect: can efficiency well and stably produce the film that the caused bad order of moisture by particle is suppressed.
In order to solve described problem, particle of the present invention is characterised in that: described particle obtains by described manufacture method of the present invention.
According to described formation, can provide the acrylic resin pellet that moisture content is low.
In order to solve described problem, acrylic resin packaging body of the present invention is characterised in that: described acrylic resin packaging body is to use moisture-vapor transmission to be less than 1.0g/m
2the material of/24h seals acrylic resin pellet and forms, and the water content of described acrylic resin pellet is less than 300ppm, and to use diameter that liquid-borne particle counter is measured be that more than 2 μ m impurity is less than 500/g.
According to described formation, can provide the acrylic resin that a kind of moisture content is low and impurity is few packaging body.
Accompanying drawing explanation
Fig. 1 means the schematic diagram that the summary of the manufacturing installation using in the manufacture method of acrylic resin pellet of present embodiment forms.
[description of reference numerals]
1-granulation device
2-carrier pipe
3-conveying air blast
4-exhaust outlet
5-storage bin
The 6-gas introduction unit that dehumidifies
7-goods are filled mouth
The specific embodiment
Below, the present invention is described in detail.In addition, in this description, " (methyl) acrylic acid " represents acrylic acid (acrylic acid) or methacrylic acid (methacrylic acid).In addition, so-called " impurity ", refers to the composition that is insoluble to chloroform (chloroform) that comprises following material: resin material that the chemical reactions such as carbonization (carbonization) generate occurs, from external environment condition, be blended into and using the inorganic matters such as mineral and salt as organic substances such as the material of main component or protein (protein) or fibers (fiber) etc. packaging body because of heat etc.Particularly, refer to that the diameter that the assay method of " impurity number " by recording in embodiment described later is measured is impurity more than 2 μ m.
In addition, " weight " and " quality " are considered as to synonym, and " % by weight " is considered as to synonym with " quality % ".In addition, represent " A～B " of scope, more than meaning A, below B.In addition, so-called " acrylic resin ", refers to the resin obtaining as the monomer component polymerization of main component containing (methyl) acrylic acid derivatives such as (methyl) acrylic acid or (methyl) acrylate.In addition, more than in this description, so-called " main component " means and contains 50 quality %.
In addition, as long as be not specifically noted, various physical property cited in this description refer to the value that the method by recording in aftermentioned embodiment is measured.
The manufacture method of the acrylic resin pellet of present embodiment comprises: forming process, is configured as particle by the acrylic resin of molten condition; Transfering process, after described forming process, by described transfer of granules in storage bin; And refrigerating work procedure, in storage bin, removing cooling described particle under wet environment; And in described transfering process, the temperature of particle is remained on more than 70 ℃.
Below, use Fig. 1 to be elaborated.
Fig. 1 means the schematic diagram that the summary of the manufacturing installation 10 using in the manufacture method of acrylic resin pellet of present embodiment forms.
As shown in Figure 1, described manufacturing installation 10 comprises: by the granulation device of acrylic resin pellet 1; By the storage bin 5 of the particle cool drying of formed thereby; And the carrier pipe 2 that described granulation device 1 is connected with storage bin 5.
For the pressure by by γ-ray emission is transported to the particle of formed thereby in storage bin 5 from granulation device 1, and be provided with on carrier pipe 2, carry with air blast 3 and carry the exhaust outlet 4 with gas.
In storage bin 5, for the particle cool drying coming will be shifted, be provided with dehumidifying gas introduction unit 6.In addition, the goods that storage bin 5 possesses for the particle after cool drying is taken out are filled mouth 7.
; in described manufacturing installation 10; utilization is from carrying the pressure with effluent air air blast 3; the particle being shaped by granulation device 1 is transferred in storage bin 5 by carrier pipe 2, and utilized from dehumidifying gas introduction unit 6 effluent air except shifted particle is cooling under wet environment.Then, from the goods of storage bin 5, fill a mouthful particle for 7 taking-up manufacturings.
(a) forming process
The method that in the forming process of present embodiment, the acrylic resin of molten condition is configured as to particle is not particularly limited, and can use previous well-known method.For example can enumerate: make to utilize the acrylic resin of the molten condition that extrusion moulding machine and template extrude to contact with water, and this resin water-cooled is solidified, then the method for cutting (line thigh patterning method); The acrylic resin of molten condition is extruded in water to the method (underwater cutting process) of cutting under the state solidifying in part generation water-cooled; The acrylic resin of cutting molten condition, then it is contacted with water and carry out the method (thermal cutting method) that water-cooled is solidified; Or by water with the vaporific acrylic resin being sprayed onto in molten condition, and the method for cutting under the state solidifying in the part generation water-cooled of this acrylic resin (water spray patterning method) etc.
The granulation device 1 using in described forming process mainly comprises: the extrusion moulding machine, template and the cutter sweep that possess the rotating shaft of single shaft or twin shaft.The cutting mode that cutter sweep adopts is such as enumerating above-described line thigh patterning method, thermal cutting method, underwater cutting process or water spray patterning method etc.In these cutting modes, can use aptly the water sprinkling pelleting machine (watering pelletizer) that adopts water spray patterning method, its reason is that the operability of this water sprinkling pelleting machine is good, and the shape of the particle of manufacturing is good.
Before in the acrylic resin that melting is mixed is supplied to template, preferably use polymer filter (polymer filter) to filter acrylic resin.That is,, by extrusion moulding machine leading section, polymer filter being set, can effectively remove impurity.
The filtering accuracy of described polymer filter is preferably in the scope more than 1 μ m, below 10 μ m, more preferably in the scope more than 1 μ m, below 5 μ m, more preferably in the scope more than 2 μ m, below 3 μ m.If filtering accuracy is less than 1 μ m, the filtration holdup time of resin in polymer filter extends so, and production efficiency reduces, so not good enough.In addition, if filtering accuracy is greater than 10 μ m, so easily sneak into impurity, so not good enough.
Described polymer filter so long as have the polymer filter of the filtering accuracy in described scope, is not particularly limited, and can use previous well-known polymer filter.Described polymer filter is such as enumerating: leaf disc type (leaf disk type) polymer filter, lamination disc-type filter (packed disk filter), cylindric style filter, candle filter (candle filter) etc.In these filters, preferably use leaf disk type polymerism thing filter, its reason is that the filter area of this leaf disk type polymerism thing filter is large, even the pressure loss (pressure loss) is also less while filtering full-bodied resin.
When described polymer filter is leaf disk type polymerism thing filter, the optimal seeking of raw and processed materials of filter comprises sintered metal fiber and the raw material of the material that obtains, comprises sintering metal powder and the raw material of the material that obtains, make wire netting lamination compression and the raw material that obtain.In these raw material, particularly preferably comprise sintered metal fiber and the raw material of the material that obtains.
In granulation device 1, the temperature of the molten resin of extruding from template can consider to make resin melting resin glass transition temperature etc. and suitably set, preferably set in the scope more than 250 ℃, below 350 ℃.If the temperature of described molten resin is in described scope, just it is deteriorated to suppress the heat of resin, and the melt viscosity of resin can be adjusted in the scope that is applicable to cutting.The temperature of described molten resin is more preferably in the scope more than 260 ℃, below 320 ℃, more preferably in the scope more than 270 ℃, below 300 ℃.
In addition, also can be between granulation device 1 and carrier pipe 2, arrange in addition and be used for the drying machine of dried particles.Described drying machine is such as enumerating whizzer etc.
After described forming process, the temperature of particle is necessary for more than 70 ℃.If the temperature of fruit granule is more than 70 ℃, just can suppress the moisture absorption of particle.After forming process, the temperature range of particle is more preferably more than 80 ℃, more preferably more than 90 ℃, most preferably more than 95 ℃.
In addition, certainly from suppressing the viewpoint of the moisture absorption shaping manufacturing procedure, preferably from shaping manufacturing procedure till the whole operation of transfering process, the temperature of particle is all more than 70 ℃.
When after described forming process, the temperature of particle is greater than glass transition temperature, can be after described forming process, before transfering process, arrange in addition and be used for the temperature of described particle to be cooled to the operation below the glass transition temperature of this particle.Cooling means about particle, is not particularly limited, and can use the previous well-known methods such as air is cooling, water cooling.
(b) transfering process
The transfering process of present embodiment is to be undertaken by utilizing the pressure of gas to transport, and the temperature of particle is remained on more than 70 ℃.
In addition, in this description so-called " transfering process ", refer to when the particle obtaining from described forming process arrives the unit of transfer particle (being carrier pipe 2 in present embodiment), during this particle arrival storage bin 5.
About described pressure, carry the gas using, be not particularly limited, such as enumerating air or nitrogen etc.Consider cost and operability, more preferably use air.Described pressure carries the absolute humidity (absolute humidity) of the gas using to be more preferably set as reduced levels, for example, below 0.05kg/kgD.A, if but remain in the temperature range of described particle, just do not need to use especially dehumidification equipment etc. to dehumidify to described gas.
Carrier pipe 2 is preferably used by milled processed etc. and removes the sanitation-grade pipe (sanitary pipe) that convex-concave in pipe face forms mirror-like.The material of carrier pipe 2 is preferably used the stainless steels (stainless steel) such as SUS304 or SUS316.
Carrier pipe 2 can be an integral body, also can use joint (joint) to form demountable formation, considers to clean and waits the easness of safeguarding (maintenance), more preferably forms the formation of using joint.Joint can be enumerated bamp joint (flange joint), screwed connection (screw joint), guide tracked joint etc., more preferably guide tracked joint, and its reason is that the delay portion of guide tracked joint is few.
The internal diameter of carrier pipe 2, carries particle above as long as the temperature of particle can be remained on to 70 ℃, is not particularly limited, more preferably in the scope more than 20mm, below 300mm.The internal diameter of carrier pipe 2 is more preferably in the scope more than 40mm, below 150mm, most preferably in the scope more than 50mm, below 100mm.When the internal diameter of carrier pipe 2 is less than 20mm, because carrying gas (pressure is carried the gas using) and the pressure loss that pipe friction causes to enlarge markedly, cause the transfer efficiency of particle significantly to reduce.In addition, when the internal diameter of carrier pipe 2 is greater than 300mm, be likely difficult to obtain sufficient conveying gas pressure.
Pressure carries the gas flow using to be more preferably set as 1.0～10.0Nm
3/ min left and right, is more preferably set in 2.0～4.0Nm
3in the scope of/min.In addition, about the transporting velocity of particle, as long as the temperature of particle can be remained on to 70 ℃, carry particle above, be not particularly limited, preferably in the scope more than 10.0m/sec, below 50.0m/sec, more preferably in the scope more than 15.0m/sec, below 30.0m/sec.By the transporting velocity of particle is set as to described scope, can suppresses Particle attrition, and carry expeditiously particle.
About particle weight in particle transport process and the weight ratio (weight of=particle weight/conveying gas of carrying gas, hereinafter referred to as " solid-gas ratio "), as long as the temperature of particle can be remained on to 70 ℃, carry above particle, be not particularly limited, preferably in the scope more than 1.0kg/kg, below 5.0kg/kg.Described weight ratio is more preferably in the scope more than 2.0kg/kg, below 3.0kg/kg.When solid-gas ratio is less than 1.0kg/kg, transfer efficiency is extremely low, and the excessive cooling effect bringing due to gas, can make particle temperature be difficult to remain on more than 70 ℃.In addition, when solid-gas ratio is greater than 5.0kg/kg, can cause Particle attrition significantly to increase because particle collides each other.
In described transfering process, the temperature of particle must remain on more than 70 ℃, from preventing the viewpoint of intergranular melting, more preferably by the Temperature Setting of particle for this reason below the glass transition temperature of particle.In addition, similarly, in described transfering process, the temperature range of particle is more preferably in the scope more than 80 ℃, below the glass transition temperature of this particle, more preferably in the scope more than 90 ℃, below the glass transition temperature of this particle, most preferably in the scope more than 95 ℃, below the glass transition temperature of this particle.
The temperature of particle in described conveying operation is remained on to the method in described preferred temperature range, for example can enumerate following methods, be not particularly limited, that is: shorten as much as possible the length of carrier pipe 2, before particle is cooling by transfer of granules to the method in storage bin 5; With heat-barrier material etc., cover carrier pipe 2 method around; Improve the method for the temperature of pressure-feed gas; And the method that these Combination of Methods are formed etc.
In addition, the exhaust outlet 4 that carrier pipe 2 possesses more preferably forms as described below, in the porch of storage bin 5, particle is separated with gas with conveying, only makes particle enter into storage bin 5.
In addition, in described explanation, for the situation of carrying out transfering process by utilizing the pressure of gas to transport, be illustrated, but the present invention is not limited to this situation.Also can adopt and use the carrying method of ribbon conveyer (belt conveyor) or the carrying method of use package conveyer (packetconveyor) etc.As long as the temperature of particle in transfering process can be remained on more than 70 ℃, just can obtain the effect roughly the same with present embodiment.
But compare with additive method, as present embodiment when utilizing the pressure of gas to transport to carry out transfering process, transfer velocity is fast, can shorten transfer time, even the transfer of long distance also can carry out easily, so effect is good especially.In addition, compare with additive method impurity in transfer process to sneak into be seldom also the reason of preferred the method.
(c) refrigerating work procedure
The refrigerating work procedure of present embodiment is in the cooling operation of described particle except shifting under wet environment in storage bin 5.In addition, in this description, so-called " storage bin ", refers to all devices such as tank (tank) (container), and its shape, material etc. are not particularly limited.
In storage bin 5, in order to seal (seal), prevent that extraneous air from entering inside, more preferably from bottom, import the gas through dehumidifying.This gas can be enumerated the inert gases such as nitrogen or air etc., if consider operability and economy, and more preferably air.Now the absolute humidity of described gas is preferably below 0.01kg/kgD.A, more preferably below 0.005kg/kgD.A.That is, the absolute humidity in storage bin 5 is preferably below 0.01kg/kgD.A, more preferably below 0.005kg/kgD.A.
The particle being housed in storage bin 5 is cooled to be less than after 70 ℃, from goods, fills mouth 7 by its taking-up and encapsulate.More preferably after being cooled to be less than 50 ℃, from goods, filling mouth 7 by its taking-up and encapsulate.
The material using about encapsulation, requires not make in fact moisture see through, and can seal.This material is such as using aptly metal container (container), evaporation to have film, polyethylene of metallic aluminium etc.The internal gas that utilization is replaced container for encapsulation through the gas of dehumidifying before encapsulation particle is also an optimal way.
More specifically, described container for encapsulation is preferably less than 1.0g/m by moisture-vapor transmission
2the formed container of material of/24hr.This material can be enumerated: thickness is the metal materials such as iron, copper, steel, the plating more than 10 μ m material that has steel-Xi thin layer, stainless steel material; Or base material is used biaxial stretch-formed polypropylene or PET (polyethyleneterephthalate) film and is coated with the film of polyvinylidene chloride (polyvinylidenechloride), film, evaporation that evaporation has aluminium, and to have film, the thickness of silica (silica) be 50 μ m allotment amount above and that may ooze out the additive of (bleed out) thin-film material such as be low-level biaxial stretch-formed polypropylene film extremely.
In addition,, when the encapsulation amount of packaged acrylic resin pellet is greater than 1t, described container for encapsulation can be used aptly and comprise at least container of described illustrative metal material more than one deck.The container that particularly preferably comprises stainless steel material.
When the encapsulation amount of acrylic resin pellet for package is 1t when following, can use aptly and comprise at least flexible container of described thin-film material more than one deck (flexiblecontainer).Particularly preferably by thering is one deck at least, use biaxial stretch-formed polypropylene or polyethylene terephthalate thin film as the formed flexible container of material of the aluminium-vapour deposition film of base material.Now, the thickness of aluminium-vapour deposition layer is preferably
above, be less than 1 μ m.
In addition, particularly preferably in the inner face of described flexible container, arrange and can carry out by heat-sealing (heatseal) materials such as polyethylene, un-stretched polypropylene of crimping.
While using the film of described sandwich construction, also adhesive linkage etc. can be set between each layer, the total film thickness of sandwich construction be preferably 80 μ m above, be less than 300 μ m.When the total film thickness of the film of described sandwich construction is less than 80 μ m, film strength is likely insufficient, and when described total film thickness is 300 μ m when above, the flexibility of film is likely not enough.The total film thickness of sandwich construction particularly preferably 90 μ m above, be less than 150 μ m.
When described container for encapsulation is, while using flexible container, preferably moisture-vapor transmission to be less than to 1.0g/m
2the described materials processing pouch of/24hr seals particle, and further by this, the container through sealing packs in the bag-shaped article shaped being formed by chemical fibre braidings such as polyethylene or polypropylene, to prevent that particle occurs damaged in preservation or course of conveying.
More than the encapsulation amount (capacity) of packaged acrylic resin pellet is preferably 100kg.This encapsulation is measured more preferably more than 300kg, more preferably more than 500kg, more than most preferably being 800kg.While manufacturing the formed bodies such as film with the packaging body that encapsulation amount is size more than 100kg, the frequency of Kaifeng encapsulation reduces, therefore except reducing ambient impurities, sneak into the possibility of particle, also can reduce the possibility that dust that the Kaifeng operation of encapsulation follows and chip are sneaked into particle.
The water content of the particle of the described method manufacturing of passing through present embodiment is preferably below 300ppm.The water content of described particle more preferably, below 200ppm, more preferably, below 100ppm, most preferably is below 50ppm.If water content is below 300ppm, just can be suppressed at resin when particle is carried out to melt-processed, decompose, or produce bubble, micropore, crazing etc., can prevent bad order.
As mentioned above, the described method by present embodiment, can obtain with moisture-vapor transmission and be less than 1.0g/m
2the material of/24h, is less than 300ppm by water content, and to use diameter that liquid-borne particle counter is measured be that more than 2 μ m impurity is less than the acrylic resin packaging body that the acrylic resin pellet of 500/g is sealed to form.
In addition, in described explanation, for carry out cool drying in storage bin 5, then situation about being encapsulated is illustrated, but the present invention is not limited to this situation.For example, can be also in storage bin 5, to carry out after cool drying transfer of granules to the mode encapsulating after other equipment, can also be not carry out encapsulating and directly carry out the mode of film shaped grade.
In addition, in described explanation, just in storage bin 5, in the situation except cooling particulate under wet environment, be illustrated, but the present invention is not limited to this situation.For example, can be also cooling particulate and directly carry out the mode of film shaped grade not.
In addition, in described explanation, the situation that possesses dehumidifying gas introduction unit 6 with regard to storage bin 5 is illustrated, but the present invention is not limited to this situation.For example, at cooling particulate not, directly carry out in the mode of film shaped grade, even if storage bin 5 does not possess dehumidifying, gas introduction unit 6 can not obtain the effect roughly the same with present embodiment yet.
In addition, in described explanation, for the bottom by from storage bin 5, import the gas through dehumidifying and except wet environment, the cooling situation of particle be illustrated, but the present invention is not limited to this situation.For example, can be also not to the interior importing gas of storage bin 5, but a part of gas in storage bin 5 is extracted out, by this gas dehumidification, and then send back to the mode that makes gas circulation such in storage bin 5.So long as can, except cooling particulate under wet environment in storage bin, just can obtain the effect roughly the same with present embodiment.
(d) acrylic resin
The acrylic resin using in present embodiment is resin that the acrylic acid as main component, methacrylic acid and these derivative polymerization are obtained and the derivative of these resins, can use previously well-known (methyl) acrylic acid series thermoplastic resin.
(methyl) acrylic acid derivative for example can be enumerated: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid chloromethyl ester, (methyl) acrylic acid-2-chloroethene ester, (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-3-hydroxy propyl ester, (methyl) acrylic acid-2,3, (methyl) acrylate such as 4,5-tetrahydroxy pentyl ester.These (methyl) acrylic acid derivatives can be used separately a kind of, also can use two or more simultaneously.In these derivatives, from optical characteristics, the excellent heat stability aspect of the resin of polymerization gained, consider most preferable methyl acrylate.
From manufacturing the viewpoint of particle under higher temperature, described acrylic resin more preferably main chain has ring structure.Can import ring structure by the N-substituted maleimide amine copolymers such as N-phenylmaleimide (N-phenylmaleimide), N-N-cyclohexylmaleimide (N-cyclohexylmaleimide), N-methyl maleimide (N-methylmaleimide) are closed, also lactonic ring (lactone ring) structure, glutaric anhydride structure, glutarimide structure etc. can be imported in strand (also referred to as in the main framing of polymer or in main chain).
In these acrylic resins, from high temperature, the difficult aspect that painted (xanthochromia) occurs of film is considered, more preferably the structure of nonnitrogenous atom.
In addition, from optical characteristics or formability, consider, more preferably main chain has the acrylic resin of lactonic ring structure.About the lactonic ring structure in main chain, can be the ring structure of 4～8 rings, but consider more preferably 5～6 rings, particularly preferably 6 rings from the stability of ring structure.In addition, the lactonic ring structure in main chain can be enumerated with following general formula (1):
[changing 1]
(in formula, R
1, R
2, R
3represent independently that respectively hydrogen atom or carbon number are organic residue of 1～20.In addition, organic residue also can contain oxygen atom)
The structure disclosing in represented structure or Japanese Patent Laid-Open 2004-168882 communique etc., polymerization yield rate is considered aspect more high when synthesizing the polymer importing before lactonic ring structure main chain, more preferably with the represented structure of general formula (1).
In addition, the organic residue in described general formula (1) is as long as carbon number is not particularly limited in 1～20 scope, such as enumerating: the thiazolinyl of the alkyl of straight chain or branch-like, straight chain or branch-like, aryl ,-OAc base ,-CN base etc.
About the acrylic resin using in present embodiment, as long as glass transition temperature, more than 70 ℃, just can be used aptly.From the viewpoint of further inhibition particle moisture absorption, the glass transition temperature of acrylic resin more preferably more than 110 ℃, more preferably more than 115 ℃, is particularly preferably more than 120 ℃, most preferably is more than 125 ℃.The glass transition temperature of acrylic resin is higher, and the temperature of particle generation melting becomes higher, therefore can at higher temperature, manufacture particle, and result can obtain the acrylic resin pellet that water content is lower.
(e) manufacture of film
The manufacture method of the film of present embodiment comprises: utilize described manufacture method to manufacture the operation of acrylic resin pellet; And described acrylic resin pellet is configured as to the operation of film.
Film shaped method can be enumerated: the well-known film shaped methods such as solution film casting method (solution casting method), extrusion by melting, rolling process (calendaring), compression forming method.In these methods, preferred solution film casting method (solution casting method), extrusion by melting.
The solvent that solution film casting method (solution casting method) is used is such as enumerating: the chlorine series solvents such as chloroform, carrene; The aromatic series series solvents such as mixed solvent of toluene (toluene), dimethylbenzene (xylene), benzene and these solvents; The alcohol series solvents such as methyl alcohol, ethanol, isopropyl alcohol, n-butanol, 2-butanols; Methyl cellosolve (methyl cellosolve), ethyl cellosolve, butyl cellosolve, dimethyl formamide (dimethy lformamide), dimethyl sulfoxide (DMSO) (dimethylsulfoxide), dioxane (dioxane), cyclohexanone (cyclohexanone), oxolane (tetrahydrofuran), acetone (acetone), ethyl acetate, ether etc.These solvents can only be used a kind of, also can use two or more simultaneously.
The device that is used for implementing solution film casting method (solution casting method) is such as enumerating rotary drum casting machine (drum casting machine), tape casting machine (band casting machine), rotary coating machine (spin coater) etc.
Extrusion by melting can be enumerated T-shaped modulus method, plavini (inflation method) etc., and now the forming temperature of film is preferably 150～350 ℃, more preferably 200～300 ℃.
In addition, for example, in order to make described film there is phase difference, can the film by described method formed thereby be stretched.
Drawing process can be used previous well-known drawing process.Such as enumerating: uniaxial tensions such as unsupported width uniaxial tension, constant width uniaxial tensions; Biaxial stretch-formed, simultaneously biaxial stretch-formed etc. biaxial stretch-formed successively; And following stretching etc., while being oriented film, the bonding shrink film of one or two sides of film and form laminate, this laminate is heated stretch processing and makes film have the convergent force in the direction with draw direction quadrature, obtain thus the birefringent film that mixes respectively existence along draw direction with the molecular group of thickness direction orientation.
From improving resistance to bending aspect, consider, described drawing process is preferably biaxial stretch-formed.In addition, the resistance to bending raising aspect two directions of the quadrature arbitrarily in making pellicular front considers, described drawing process is preferably simultaneously biaxial stretch-formed.In addition, from realize simultaneously any direction in face resistance to bending, with larger face in phase difference value aspect consider, described drawing process is preferably biaxial stretch-formed successively.Two directions of the quadrature arbitrarily in face, for example, can enumerate with slow axis in pellicular front and be parallel direction and be vertical direction with slow axis in pellicular front.In addition, can suitably set the stretching conditions such as stretching ratio, draft temperature, draw speed according to required phase difference value, required resistance to bending, be not particularly limited.
The device stretching etc. for example can be enumerated cylinder stretching-machine, tentering (tenter) type stretching-machine, small test can be enumerated cupping machine, uniaxial tension machine, biaxial stretch-formed machine, biaxial stretch-formed machine etc. simultaneously successively with stretching device, uses any device in these all can obtain the phase-contrast film of present embodiment.
About draft temperature, preferably near being the glass transition temperature of particle, film raw material stretches.Particularly, preferably at (glass transition temperature-30) ℃～(glass transition temperature+50) ℃, stretch, more preferably (glass transition temperature-20) ℃～(glass transition temperature+20) ℃, more preferably (glass transition temperature-10) ℃～(glass transition temperature+10) ℃.If described draft temperature, lower than (glass transition temperature-30) ℃, cannot obtain sufficient stretching ratio, so not good enough.If described draft temperature is higher than (glass transition temperature+50) ℃, resin can occur to flow and cause carrying out stable stretching, so not good enough.
Preferably take the defined stretching ratio of Area Ratio as the scope of 1.1～25 times, more preferably 1.2～10 times scope, more preferably in the scope of 1.3～5 times, stretch.If described stretching ratio is less than 1.1 times, along with stretching, cannot shows phase difference performance and improve toughness, so not good enough.If described stretching ratio is greater than 25 times, cannot confirm the effect corresponding with improving stretching ratio.
When stretching to a direction, preferably the stretching ratio with respect to this direction be the scope of 1.05～10 times, more preferably 1.1～5 times scope, more preferably in the scope of 1.2～3 times, stretch.If described stretching ratio is less than 1.05 times, sometimes cannot obtain required phase difference value, so not good enough.If described stretching ratio is greater than 10 times, cannot confirm the effect corresponding with improving stretching ratio, and sometimes in drawing process film can rupture, so not good enough.
Draw speed (direction) is the scope of 10～20000%/min, the more preferably scope of 100～10000%/min preferably.If draw speed is slower than 10%/min, obtain sufficient stretching ratio and need to spend the longer time, manufacturing cost improves, so not good enough.If draw speed is faster than 20000%/min, likely there is fracture etc. in oriented film, so not good enough.
The stretching of described film comprises: the operation of first stage, stretches at the temperature more than the glass transition temperature of non-stretched film; And the operation of the second stage of carrying out after the operation of first stage, in the temperature range of glass transition temperature+20 of glass transition temperature-10 of this film ℃～this film ℃, stretch; More preferably make the first stage operation draft temperature than the draft temperature of the operation of second stage high 5 ℃ with on stretch.
As long as the draft temperature of the operation of described first stage is more than the glass transition temperature for non-stretched film, be not particularly limited, more preferably the temperature range of glass transition temperature+40 of the glass transition temperature of this film～this film ℃, more preferably the temperature range of glass transition temperature+30 of glass transition temperature+2 of this film ℃～this film ℃, the particularly preferably temperature range of glass transition temperature+25 of glass transition temperature+5 of this film ℃～this film ℃.
If the draft temperature of the operation of described first stage is lower than the glass transition temperature of described film, likely in the operation of first stage, show phase difference, and the phase difference of direction in face is eliminated in the stretching of the operation of second stage, so the phase difference value of last obtained film reduces.In addition, if the draft temperature of the operation of described first stage higher than glass transition temperature+40 ℃ of described film, likely resin easily flows, and is difficult to stably stretch.
In addition, in described record, draft temperature is the temperature difference being expressed as with respect to the glass transition temperature of non-stretched film sometimes.Now, for example " glass transition temperature+40 ℃ ", mean than the temperature of high 40 ℃ of glass transition temperature, " glass transition temperature-10 ℃ ", mean than the temperature of low 10 ℃ of glass transition temperature.
The stretching ratio of the operation of described first stage is preferably in the scope of 1.1～25 times, more preferably in the scope of 1.2～10 times, more preferably in the scope of 1.3～5 times.When stretching ratio is during lower than 1.1 times, likely the raising degree of flexibility is little, when stretching ratio is during higher than 25 times, likely improve the effect that stretching ratio brings and reduce, and in drawing process, film easily produces fracture.
The draw speed of the operation of described first stage is preferably in the scope of 10～20000%/min, more preferably in the scope of 100～10000%/min.If draw speed is slower than 10%/min, to completing to stretch, to spend before for a long time, so manufacturing cost can improve.If draw speed is faster than 20000%/min, oriented film likely produces fracture etc.
The draft temperature of the operation of described second stage is preferably the temperature range of glass transition temperature+20 ℃ of glass transition temperature-10 ℃～this film of non-stretched film, more preferably the temperature range of glass transition temperature+15 of glass transition temperature-10 of this film ℃～this film ℃, the more preferably temperature range of glass transition temperature+15 of glass transition temperature-5 of this film ℃～this film ℃.
If the draft temperature of the operation of described second stage, lower than glass transition temperature-10 ℃ of described film, likely cannot stretch with sufficient stretching ratio.In addition, if the draft temperature of the operation of described second stage higher than glass transition temperature+20 ℃ of described film, likely orientation is insufficient for the polymer in film, and cannot make film have required phase difference.
The stretching ratio of the operation of described second stage is preferably in the scope of 1.1～25 times, more preferably in the scope of 1.2～10 times, more preferably in the scope of 1.3～5 times.When stretching ratio is during lower than 1.1 times, likely the raising degree of flexibility is little, when stretching ratio is during higher than 25 times, likely improve the effect that stretching ratio brings and reduce, and in drawing process, film easily ruptures.
The draw speed of the operation of described second stage is preferably in the scope of 10～20000%/min, more preferably in the scope of 100～10000%/min.If draw speed is slower than 10%/min, to completing to stretch, to spend before for a long time, so manufacturing cost improves.If draw speed is faster than 20000%/min, likely there is fracture etc. in oriented film.
In described drawing process, the draft temperature of the operation of first stage is higher more than 5 ℃ than the draft temperature of the operation of second stage.By carrying out the operation of first stage at than the high temperature of the operation of second stage, in the operation of first stage, can not make film there is larger phase difference, and can make film there is the flexibility to the bending on the axle with draw direction quadrature.Then, by carrying out the operation of second stage at than the low temperature of the operation of first stage, can further make film there is the flexibility to arbitrary axis, and can obtain the large phase-contrast film of phase difference value in face.
At this, when the draft temperature of the operation of first stage is less than draft temperature+5 ℃ of operation of second stage, be likely difficult to realize simultaneously make film have flexibility to arbitrary axis, with required phase difference value.In addition, in order to increase phase difference in the face of giving film, preferably under lower temperature, carry out the stretching of the operation of second stage.And by making the draft temperature of operation of first stage higher more than 5 ℃ than the draft temperature of the operation of second stage, while carrying out the stretching of operation of second stage, film is not easy to rupture.
In addition, in described drawing process, preferably the stretching ratio of second stage is greater than the stretching ratio of the operation of first stage.If more than the stretching ratio of the operation that the stretching ratio of the operation of first stage is second stage, be likely difficult to realize simultaneously make film have flexibility to arbitrary axis, with required phase difference value.
In described drawing process, preferably in the operation of second stage, along the direction of the draw direction quadrature of the operation with the first stage, stretch.Now, can make fully film there is the flexibility to the bending of arbitrary axis.
As mentioned above, the manufacture method of acrylic resin pellet of the present invention is characterised in that and comprises: forming process, is configured as particle by the acrylic resin of molten condition; And transfering process, after described forming process, by described transfer of granules in storage bin; And in described transfering process, the temperature of particle is remained on more than 70 ℃.
So, even if given play to, adopt the so bibulous resin of acrylic resin, also can efficiency well and stably manufacture the effect of the particle that moisture content is low.
In addition, as mentioned above, the manufacture method of film of the present invention is characterised in that and comprises: utilize described manufacture method of the present invention to manufacture the operation of acrylic resin pellet; And described acrylic resin pellet is configured as to the operation of film.
So, given play to the effect of can efficiency well and stably manufacturing the film that bad order that the moisture because of particle causes is suppressed.
[embodiment]
Below, according to embodiment, illustrate in greater detail the present invention, but the present invention is not limited to following embodiment.In embodiment and comparative example shown below, be to manufacture particle with the manufacturing installation 10 shown in described Fig. 1.In addition, be provided with whizzer (not shown) in described manufacturing installation, it is configured to: to particle cut, water-cooled utilizes whizzer to dehydrate after solidifying, then by particle transport in storage bin 5.
In addition, unless otherwise specified, " ppm " in embodiment all represents the value of trying to achieve with mass conversion, for example 10, and 000ppm represents 1 quality %.In addition, in following embodiment and comparative example, carry the temperature of the air using to be about 25～28 ℃, humidity is about 40～60%.
< glass transition temperature (Tg) >
The glass transition temperature of particle (Tg) is that at sample, to be about 10mg, programming rate be under 10 ℃/min, the nitrogen flow condition that is 50cc/min, use DSC (differentialscanning calorimeter, differential scanning calorimeter) (Rigaku limited company manufactures, device name: DSC-8230), also try to achieve by mid-point method (midpoint method) according to ASTM-D-3418.
< particle water content >
Use and (the Mitsubishi Chemical Ind's manufacture of moisture vapourizing unit, VA-100) (Mitsubishi Chemical Ind manufactures the determination of trace water device connecting, CA-100), by Ka Er Fischer (KarlFischer) volumetric precipitation method, obtain the water content of particle.In detail, after the about 1.0g particle of accurate weighing, imported in the described moisture vapourizing unit that temperature remains on 250 ℃ and heated 2 minutes.Utilize the nitrogen of the drying by phosphorus pentoxide (phosphorus pentoxide) that whole moisture of this place generation are imported in described moisture vapourizing unit, and try to achieve water content by Ka Er Fischer volumetric precipitation method.
In addition, water content is to adopt following value: produce 0.5t continuously under the condition of each embodiment described later and comparative example more than, and every 200kg is sampled to the mean value of water content of the particle of (sampling) and acquisition.
< melt granules content >
From the entrance that is located at storage bin 5 funnel (hopper, not shown) nearby, take out 1kg particle, carry out visual examination, by the quality of the particle of melting, carry out mass conversion and try to achieve melt granules content (ppm).
< particle temperature >
At drum type brake Dewar vacuum flask, (capacity is 2,000ml, external diameter is 125mm, internal diameter is 100mm, the degree of depth is 280mm) in pack the particle of 1,300g into, in this bottle by hypsothermometer (measurement range: 0 ℃～200 ℃, the about 300mm of total length) insert 150mm, obtain to place and be up to Da Wendu as the temperature of particle after 10 minutes.
< particle weight >
Measure the weight of 10 particles and try to achieve mean value, thereby obtaining particle weight.
< lactonic ring structural units containing proportional >
The weight reduction being produced when whole hydroxyls are departed from from the composition of the polymer that obtains by polymerization with the form of methyl alcohol is made as benchmark, by dynamic TG (dynamicthermogravimetry, Dynamic Thermal gravimetric method) till 300 ℃ before starting to decompose to polymer in measuring from starting to occur before reducing 150 ℃ of weight by the caused weight reduction of dealcoholization, obtain dealcoholization rate (lactonic ring rate).
That is, during the dynamic TG that is determined at the polymer with lactonic ring structure measures from 150 ℃ to the weight slip during till 300 ℃, obtained actual measurement weight slip is made as to (X).On the other hand, whole hydroxyls contained during hypothesis polymer is formed form alcohol because participating in forming lactonic ring, thereby the theoretical weight slip while departing from the composition of polymer since then (, suppose to produce 100% dealcoholization in the composition of polymer and the weight slip that calculates) is made as (Y).In addition, more specifically, the mol ratio of the starting monomer with the structure (hydroxyl) that participates in dealcoholization that can be in polymer, be that the containing ratio of the described starting monomer during this polymer forms is calculated theoretical weight slip (Y).These are worth to (X, Y) substitution dealcoholysis calculating formula:
1-(actual measurement weight slip (X)/theoretical weight slip (Y))
Obtain its value, and represent with %, obtain thus dealcoholization rate.
As one example, calculate the shared ratio of lactonic ring structure in the particle of gained in polymerization example described later.The theoretical weight slip (Y) of this polymer is obtained in trial, because the molecular weight of methyl alcohol is 32, the molecular weight of 2-(hydroxymethyl) methyl acrylate is 116, the containing ratio (weight ratio) of the 2-before lactone cyclisation in polymer (hydroxymethyl) methyl acrylate is 20 quality % on forming, so theoretical weight slip (Y) is (32/116) * 20 ≈ 5.52 quality %.On the other hand, by dynamic TG, measuring the actual measurement weight slip (X) obtaining is 0.18 quality %.By in dealcoholysis calculating formula described in these value substitutions, obtain 1-(0.18/5.52) ≈ 0.967, so dealcoholization rate is 96.7%.
Then, suppose only with described dealcoholization rate, to have carried out lactone cyclization, by following formula, calculate lactonic ring containing proportional:
Lactonic ring contain ratio (quality %)=B * A * M
r/ M
m
(in formula, B is in the polymer before lactone cyclisation, has the quality of starting monomer structural units of the structure (hydroxyl) that participates in lactone cyclisation containing proportional, M
rfor the formula weight of generated lactonic ring structural units, M
mfor having the molecular weight of the starting monomer of the structure (hydroxyl) that participates in lactone cyclisation, A is dealcoholization rate).
For example, during for the situation of aftermentioned polymerization example, containing ratio from the structure of 2-(hydroxymethyl) methyl acrylate in the polymer of acrylic resin before lactone cyclisation is 20.0 quality %, the dealcoholization rate calculating is 96.7%, the formula weight of the lactonic ring structural units that molecular weight generates while being 116 2-(hydroxymethyl) methyl acrylate and methyl methacrylate condensation is 170, thus in acrylic resin lactonic ring containing proportional be 28.3 (=20.0 * 0.967 * 170/116) quality %.
< moisture-vapor transmission >
Moisture-vapor transmission refers to " in temperature, being under 40 ℃, the humidity condition that is 90%RH, the amount of the steam by unit are sample in the unit interval ", and it is that agar diffusion method (cup method) by recording in JIS Z0208 is measured.
< impurity is counted >
By 5g grain dissolution, in the chloroform of 100mL, (PARTIKEKMESS-UND ANALYSESYSTEME GMBH company manufactures, and SVSS), measuring diameter in every 1g solution is the quantity of impurity more than 2 μ m to use liquid-borne particle counter.In addition, in mensuration Shi clean room (cleanroom), carry out.
[polymerization example]
In the reactor with agitating device, temperature sensor, condenser, nitrogen ingress pipe, drop into 2-(hydroxymethyl) methyl acrylate 20 mass parts, methyl methacrylate 80 mass parts, toluene 100 mass parts, one side passes into nitrogen and is simultaneously warmed up to 105 ℃.After backflow starts, add the different n-nonanoic acid tert-pentyl ester (trade name: Lupasol570 of peroxidating as initator, ArkemaYoshitomi limited company manufactures) 0.1 mass parts, meanwhile, one side is lasted 2 hours and is dripped the solution that comprises different n-nonanoic acid tert-pentyl ester 0.2 mass parts of peroxidating and toluene 1 mass parts, one side is carried out polymerisation in solution at 105 ℃～110 ℃, then lasts 4 hours and carries out aging (ageing).In obtained polymer solution, add phosphoric acid stearyl ester/di(2-ethylhexyl)phosphate stearyl ester mixture (trade name: PhoslexA-18, Sakai chemistry limited company manufactures) 0.1 mass parts, under refluxing, with 100～110 ℃, carry out 5 hours cyclized condensation reactions.
[embodiment 1]
In the present embodiment; granulation device 1 is exhaust cellular type screw extruder (the vent-type screw extruder that uses biaxially oriented engagement system; JSW manufactures; screw diameter (D): 120mm; cylinder length (L): 5,460mm, L/D=44.5; exhaust hole count: 4 (1 final vacuum hole (rear vent), 3 front-seat pores (fore vent))).In addition, upper at the extrusion die (extruder die) of being located at the cylinder front end of extruder, along circumference, be formed through the micropore that a plurality of diameters are 4mm, and the cutter of water spray cutting mode is installed.And, there is following formation: the dehydration equipment (not shown) comprise whizzer is set after cutting, water-cooled are solidified, then utilizes gas to carry, and by particle transport in storage bin 5.
Utilize gear pump (gear pump), the acrylic resin obtaining in polymerization example is passed through in static mixer (static mixer) formula heat exchanger, thereby this acrylic resin is heated to 240 ℃, utilizes pressure-regulating valve to make pressure remain on 20kg/cm
2afterwards, described acrylic resin is supplied to by bucket (barrel) Temperature Setting in the extruder of 270 ℃.So that extruder the 1st, the 2nd, the vacuum of the 3rd steam vent mode that reaches respectively 250mmHg, 20mmHg, 20mmHg operates, and the volatile ingredient in resin is removed, then make resin pass through the polymer filter (filtering accuracy: 5 μ m) of leaf disc type, the mould mouth (micropore) of then take 400kg/h, being 4mm from the diameter that extrusion die was had in continuous 3 hours is extruded the acrylic resin of molten condition, and after carrying with the condition of table 1 record, in storage bin 5, be cooled to below 50 ℃, manufacture thus particle.
The temperature of measuring mould mouth exit acrylic acid series polymeric compounds, result is 290 ℃, and the temperature of nearby locating the particle of (funnel top) sampling at the entrance of storage bin 5 is 105 ℃, can confirm in transfering process the temperature of particle remain on 70 ℃ above.In addition, melt granules amount is considerably less, is 140ppm, so infer that the temperature of particle in transfering process is to remain on below the glass transition temperature of particle.The water content of the described particle sampling on funnel top in addition, is 25ppm.In addition, be cooled to 50 ℃ following after, the water content of the particle taking out from storage bin is 30ppm, impurity number is 320/g.
[embodiment 2]
The acrylic resin of extruding molten condition from mould mouth with 280kg/h, continuous 3 hours replaces with 400kg/h, the continuous acrylic resin of extruding molten condition for 3 hours from mould mouth, in addition, carries out the operation identical with embodiment 1 and manufactures particle.
As a result, after the condition of recording with table 1 is carried, the temperature of the particle sampling on funnel top is 100 ℃, can confirm that in transfering process, the temperature of particle remains on 70 ℃ above.In addition, melt granules amount is 0ppm, and the temperature of inferring particle in transfering process is to remain on below the glass transition temperature of particle.In addition, the water content of described particle is 30ppm, and impurity number is 290/g.
[embodiment 3]
The average weight of particle is changed to 25mg, and the rotating speed of whizzer is made as to 70% of embodiment 1, thus the particle temperature before storage tank is changed to 70 ℃, in addition, carry out the operation identical with embodiment 1 and manufacture particle.
As a result, after the condition of recording with table 1 is carried, the temperature of the particle sampling on funnel top is 70 ℃, can confirm that in transfering process, the temperature of particle remains on 70 ℃ above.In addition, melt granules amount is 0ppm, and the temperature of inferring particle in transfering process is to remain on below the glass transition temperature of particle.In addition, the water content of described particle is 280ppm, and impurity number is 250/g.
[embodiment 4]
In the present embodiment, resin is to use in the particle of embodiment 1 manufacturing of 90 mass parts, and dry type is mixed AS resin (acrylonitrile-styreneresin, the acrylonitrile-styrene resin of (dry blend) 10 mass parts; Trade name: Stylac AS384, chemical company of Asahi Chemical Industry manufactures) and the resin of acquisition.In addition, extruder is to use single axle extruding machine (screw diameter (D): 50mm, cylinder length (L): 1,800mm, L/D=36.5, exhaust hole count: 1).
Cylinder front end at extruder; be provided with leaf disk type polymerism thing filter (filtering accuracy: 5 μ m); on the extrusion die in exit of being located at this polymer filter; be formed through the micropore that diameter is 3mm; the strand form thing spuing from these micropores is directed in tank and after in addition water-cooled is solidified, by line thigh cutting mode, carries out granulating.Dehydration procedure is not set after granulating especially, directly utilizes gas to carry, and particle transport is arrived to storage place.
So that barrel temperature reaches the mode that 250 ℃, steam vent vacuum reach 100mmHg, operate and volatile ingredient removed, from mould mouth with the speed of the 100kg/h particle that spues.The resin temperature of measuring mould mouth exit, result is 275 ℃, after the condition of being recorded with table 1 is carried, the temperature of the particle sampling on funnel top is 97 ℃, can confirm that in transfering process, the temperature of particle remains on 70 ℃ above.In addition, melt granules amount is considerably less, is 100ppm, so infer that the temperature of particle in transfering process is to remain on below the glass transition temperature of particle.In addition, the moisture content of described particle is 150ppm, and impurity number is 400/g.
[embodiment 5]
Except the rotating speed of whizzer is made as embodiment 1 70%, carry out the operation identical with embodiment 1 and manufacture particle.
As a result, after the condition of recording with table 1 is carried, the temperature of the particle sampling on funnel top is 82 ℃, can confirm that in transfering process, the temperature of particle remains on 70 ℃ above.In addition, melt granules amount is 0ppm, and the temperature of inferring particle in transfering process is to remain on below the glass transition temperature of particle.In addition, the water content of described particle is 95ppm, and impurity number is 300/g.
[comparative example 1]
With the speed of 50kg/h, continuous 10 hours, from the spue acrylic resin of molten condition of mould mouth, replace with the speed of 100kg/h from the spue acrylic resin of molten condition of mould mouth, in addition, carry out the operation identical with embodiment 4 and manufacture particle.The results are shown in table 1.The impurity number of described particle is 480/g.
[table 1]
[embodiment 7]
By the acrylic resin pellet of embodiment 1 manufacturing, the encapsulation amount of 600kg of take is sealed to moisture-vapor transmission as 0.8g/m
2in the three-layer thin-film of polyethylene/aluminium-vapour deposition layer/polypropylene film of/24hr (thickness is 100 μ m).
In the warehouse with roof, keeping is after 1 year, and the amount of moisture of acrylic resin pellet is 80ppm, and impurity number is 330/g, and moisture, impurity number all maintain good value.
[embodiment 8]
By the acrylic resin pellet of embodiment 1 manufacturing, the encapsulation amount of 400kg of take is sealed to moisture-vapor transmission as 0.8g/m
2in the three-layer thin-film of the PET of/24hr (PET)/aluminium-vapour deposition layer/polypropylene film (thickness is 100 μ m).
In the warehouse with roof, keeping is after 1 year, and the amount of moisture of acrylic resin pellet is 70ppm, and impurity number is 340/g, and moisture, impurity number all maintain good value.
[comparative example 2]
By the acrylic resin pellet of embodiment 1 manufacturing, the encapsulation amount of 20kg of take is sealed to moisture-vapor transmission as 10g/m
2in the bilayer film of nylon/polyethylene of/24hr (thickness is 120 μ m).
In the warehouse with roof, keeping is after one month, and the amount of moisture of acrylic resin pellet is 1,500ppm, and impurity number is 330/g, and moisture significantly rises.
[comparative example 3]
By the acrylic resin pellet of embodiment 1 manufacturing, the encapsulation amount of 20kg of take is sealed to moisture-vapor transmission as 300g/m
2in brown paper more than/24hr (kraft paper).
In the warehouse with roof, keeping is after three days, and the amount of moisture of acrylic resin pellet is 15,000ppm, and impurity number is 1,200/g, and moisture, impurity number all significantly rise.
The present invention is not limited to each described embodiment, can in the scope shown in claim, carry out various changes, and the embodiment technological means that disclosed separately in different embodiments is appropriately combined and that obtain is also included in the technical scope of the present invention.
(industrial utilizability)
The manufacture method of acrylic resin pellet of the present invention, even if adopt the bibulous resins such as acrylic resin, also can efficiency well and stably manufacture the particle that moisture content is low.So, can be applied in the past in known various particle.
Claims (10)
1. a manufacture method for acrylic resin pellet, is characterized in that, comprising:
Forming process, is configured as particle by the acrylic resin of molten condition, and
Transfering process, after described forming process, by described transfer of granules in storage bin; And,
In the main chain of described acrylic resin, there is ring structure,
In described transfering process, the temperature of particle is remained on more than 70 ℃.
2. the manufacture method of acrylic resin pellet according to claim 1, is characterized in that, the glass transition temperature of described acrylic resin is more than 110 ℃.
3. according to the manufacture method of the acrylic resin pellet described in any one in claim 1 or 2, it is characterized in that, described ring structure is for selecting freedom to close at least one in the group of the ring structure, lactonic ring structure, glutaric anhydride structure and the glutarimide structure composition that import by N-substituted maleimide amine copolymer.
4. a manufacture method for film, is characterized in that, comprising:
The operation of acrylic resin pellet is manufactured in utilization according to the manufacture method described in any one in claim 1-3; And
Described acrylic resin pellet is configured as to the operation of film.
5. an acrylic resin pellet, is characterized in that, by obtaining according to the manufacture method described in any one in claim 1-3.
6. an acrylic resin packaging body, is characterized in that,
Described acrylic resin packaging body is to use moisture-vapor transmission to be less than 1.0g/m
2the material of/24h seals acrylic resin pellet and forms,
Form in the main chain of acrylic resin of described acrylic resin pellet and there is ring structure,
The water content of described acrylic resin pellet is less than 300ppm, and to use diameter that liquid-borne particle counter is measured be that more than 2 μ m impurity is less than 500/g.
7. acrylic resin packaging body according to claim 6, is characterized in that, described moisture-vapor transmission is less than 1.0g/m
2the material of/24h is that to select free thickness be more than 10 μ m iron, copper, steel, plating by the metal material of the material of steel-Xi thin layer, group that stainless steel material forms, with acrylic resin pellet described in the seal of vessel that contains at least one more than one deck above-mentioned metal material.
8. acrylic resin packaging body according to claim 6, is characterized in that, described moisture-vapor transmission is less than 1.0g/m
2the material of/24h is that to select free base material to use biaxial stretch-formed polypropylene or polyethylene terephthalate thin film and be coated with the film, evaporation of polyvinylidene chloride be the thin-film material of the group that forms of biaxial stretch-formed polypropylene films more than 50 μ m by the film of aluminium, evaporation by film, the thickness of silica, and the flexible container that use contains at least one more than one deck above-mentioned thin-film material seals described acrylic resin pellet.
9. acrylic resin packaging body according to claim 6, is characterized in that, the glass transition temperature that forms the acrylic resin of described acrylic resin pellet is more than 110 ℃.
10. acrylic resin packaging body according to claim 6, it is characterized in that, described ring structure is for selecting freedom to close at least one in the group of the ring structure, lactonic ring structure, glutaric anhydride structure and the glutarimide structure composition that import by N-substituted maleimide amine copolymer.
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| CN114536583A (en) * | 2022-01-17 | 2022-05-27 | 中山市武汉理工大学先进工程技术研究院 | Thermoplastic resin high-temperature melt extrusion molding and granulating method capable of sufficiently removing oxygen |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4819952B2 (en) * | 2007-08-21 | 2011-11-24 | 株式会社日本触媒 | Acrylic resin package |
| JP5592713B2 (en) * | 2010-06-25 | 2014-09-17 | 旭化成ケミカルズ株式会社 | Pellet manufacturing method |
| JP5650960B2 (en) * | 2010-09-06 | 2015-01-07 | 積水化学工業株式会社 | Method for producing foamable thermoplastic resin masterbatch |
| DE102011018403A1 (en) * | 2011-04-21 | 2012-10-25 | Automatik Plastics Machinery Gmbh | Process for the preparation of pharmaceutical products from a melt material |
| JP5987526B2 (en) * | 2012-07-25 | 2016-09-07 | 三菱レイヨン株式会社 | Acrylic resin pellet manufacturing method and acrylic resin molded body |
| JP2014063031A (en) * | 2012-09-21 | 2014-04-10 | Konica Minolta Inc | Optical film and production method of optical film |
| JP6006653B2 (en) * | 2013-02-04 | 2016-10-12 | 出光興産株式会社 | Polycarbonate resin extrusion granulator and polycarbonate resin extrusion granulation method |
| US10052806B2 (en) | 2014-03-31 | 2018-08-21 | Toray Industries, Inc. | Manufacturing apparatus and manufacturing method for liquid crystalline polyester resin pellets |
| DE102018222523A1 (en) * | 2018-12-20 | 2020-06-25 | Robert Bosch Gmbh | Brake system damper device |
| JP7330809B2 (en) | 2019-08-09 | 2023-08-22 | 株式会社ジャパンディスプレイ | Electronics |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH091547A (en) * | 1995-06-21 | 1997-01-07 | Sumitomo Chem Co Ltd | Method for producing methacrylic resin pellets |
| JP2000053708A (en) * | 1998-08-06 | 2000-02-22 | Asahi Chem Ind Co Ltd | Production of methacrylic polymer with excellent production stability |
| JP2005082716A (en) * | 2003-09-09 | 2005-03-31 | Mitsubishi Rayon Co Ltd | Methacrylic polymer and its manufacturing method |
| JP2007063541A (en) * | 2005-08-04 | 2007-03-15 | Nippon Shokubai Co Ltd | Low birefringent copolymer |
| CN101228198A (en) * | 2005-08-04 | 2008-07-23 | 株式会社日本触媒 | Low birefringent copolymer |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0737026B2 (en) * | 1988-05-17 | 1995-04-26 | 三井・デュポンポリケミカル株式会社 | Resin pellet manufacturing method |
| JP2600116Y2 (en) * | 1993-10-19 | 1999-10-04 | 日本エステル株式会社 | Transfer device for polyester pellets |
| JPH10291584A (en) * | 1997-04-22 | 1998-11-04 | Showa Packs Kk | Large-sized highly moisture-proof bag for housing moisture absorbent content, and its forming method |
| JPH11226945A (en) * | 1998-02-10 | 1999-08-24 | Mitsubishi Rayon Co Ltd | Method for pelletizing acrylic resin, device for pelletizing acrylic resin, and manufacture of acrylic film |
| EP1095954A4 (en) | 1998-06-17 | 2003-04-23 | Mitsubishi Rayon Co | Impact-resistant acrylic polymer pellets and process for producing them |
| JP2002002616A (en) * | 2000-06-20 | 2002-01-09 | Dainippon Ink & Chem Inc | Masterbatch packaging method |
| JP3718627B2 (en) * | 2000-10-20 | 2005-11-24 | 帝人化成株式会社 | Storage method of polycarbonate resin for wet molding |
| JP4157333B2 (en) * | 2001-07-03 | 2008-10-01 | 株式会社日本触媒 | Continuous production method of surface-modified water-absorbent resin powder |
| JP2006124443A (en) | 2004-10-27 | 2006-05-18 | Banso:Kk | Acrylic resin composition, method for producing the same, soft acrylic resin and method for producing the same |
| JP4819952B2 (en) * | 2007-08-21 | 2011-11-24 | 株式会社日本触媒 | Acrylic resin package |
-
2008
- 2008-08-08 JP JP2009529005A patent/JP4819952B2/en active Active
- 2008-08-08 KR KR1020117013117A patent/KR101552378B1/en active IP Right Grant
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH091547A (en) * | 1995-06-21 | 1997-01-07 | Sumitomo Chem Co Ltd | Method for producing methacrylic resin pellets |
| JP2000053708A (en) * | 1998-08-06 | 2000-02-22 | Asahi Chem Ind Co Ltd | Production of methacrylic polymer with excellent production stability |
| JP2005082716A (en) * | 2003-09-09 | 2005-03-31 | Mitsubishi Rayon Co Ltd | Methacrylic polymer and its manufacturing method |
| JP2007063541A (en) * | 2005-08-04 | 2007-03-15 | Nippon Shokubai Co Ltd | Low birefringent copolymer |
| CN101228198A (en) * | 2005-08-04 | 2008-07-23 | 株式会社日本触媒 | Low birefringent copolymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114536583A (en) * | 2022-01-17 | 2022-05-27 | 中山市武汉理工大学先进工程技术研究院 | Thermoplastic resin high-temperature melt extrusion molding and granulating method capable of sufficiently removing oxygen |
Also Published As
| Publication number | Publication date |
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| WO2009025192A1 (en) | 2009-02-26 |
| KR20100044734A (en) | 2010-04-30 |
| JPWO2009025192A1 (en) | 2010-11-25 |
| KR20110069896A (en) | 2011-06-23 |
| CN101765488A (en) | 2010-06-30 |
| CN104057554B (en) | 2016-08-17 |
| TWI494353B (en) | 2015-08-01 |
| TW200911891A (en) | 2009-03-16 |
| JP2011183817A (en) | 2011-09-22 |
| JP2011235655A (en) | 2011-11-24 |
| KR101172967B1 (en) | 2012-08-09 |
| KR101552378B1 (en) | 2015-09-10 |
| JP4819952B2 (en) | 2011-11-24 |
| JP4815025B2 (en) | 2011-11-16 |
| CN101765488B (en) | 2016-05-25 |
| JP5318926B2 (en) | 2013-10-16 |
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