JP2018177849A - Vinylidene chloride resin composition, and resin blend - Google Patents
Vinylidene chloride resin composition, and resin blend Download PDFInfo
- Publication number
- JP2018177849A JP2018177849A JP2017074327A JP2017074327A JP2018177849A JP 2018177849 A JP2018177849 A JP 2018177849A JP 2017074327 A JP2017074327 A JP 2017074327A JP 2017074327 A JP2017074327 A JP 2017074327A JP 2018177849 A JP2018177849 A JP 2018177849A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- vinylidene chloride
- plasticizer
- chloride resin
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011347 resin Substances 0.000 title claims abstract description 128
- 229920005989 resin Polymers 0.000 title claims abstract description 128
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000011342 resin composition Substances 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims description 36
- 239000004014 plasticizer Substances 0.000 claims abstract description 86
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 65
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 65
- -1 hydrotalcite compound Chemical class 0.000 claims description 42
- 239000002699 waste material Substances 0.000 claims description 17
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 10
- 229960001545 hydrotalcite Drugs 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 7
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 229920006127 amorphous resin Polymers 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 239000003017 thermal stabilizer Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 230000000704 physical effect Effects 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 15
- 239000012760 heat stabilizer Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 2
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000012773 agricultural material Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229920006038 crystalline resin Polymers 0.000 description 2
- 229940100539 dibutyl adipate Drugs 0.000 description 2
- 229940031769 diisobutyl adipate Drugs 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- YPDXSCXISVYHOB-UHFFFAOYSA-N tris(7-methyloctyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCC(C)C)C(C(=O)OCCCCCCC(C)C)=C1 YPDXSCXISVYHOB-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- LSWRBVSEWBWTDR-UHFFFAOYSA-N 2-hydroxyethyl benzoate Chemical compound OCCOC(=O)C1=CC=CC=C1 LSWRBVSEWBWTDR-UHFFFAOYSA-N 0.000 description 1
- NIYZIKWNKMOAFD-UHFFFAOYSA-N 6-octan-3-yloxy-6-oxohexanoic acid Chemical compound CCCCCC(CC)OC(=O)CCCCC(O)=O NIYZIKWNKMOAFD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、塩化ビニリデン樹脂組成物、及び樹脂ブレンド物に関する。 The present invention relates to vinylidene chloride resin compositions and resin blends.
塩化ビニリデン樹脂は、耐熱性、ガスバリヤー性、難燃性、耐薬品性等の有用な機能的特性を有する樹脂である。塩化ビニリデン樹脂は、非常に熱安定性が悪く、且つ汎用加工法における加工温度の範囲が狭いため、加工が困難であることが知られている。例えば、塩化ビニリデン樹脂は、塩化ビニル樹脂用の汎用的な熱安定剤を用いた場合、押出加工温度の範囲である１５０〜１８０℃では１０分前後で急速に脱塩酸反応を起こし、劣化、黒化してしまう（例えば、下記の特許文献１参照）。このため、塩化ビニリデン樹脂の加工には、加工を行うためには特殊な設備、あるいは特殊な添加剤が必要とされる。 Vinylidene chloride resin is a resin having useful functional properties such as heat resistance, gas barrier property, flame retardancy, chemical resistance and the like. Vinylidene chloride resins are known to be difficult to process because they have very poor thermal stability and a narrow range of processing temperatures in general-purpose processing. For example, when a general-purpose heat stabilizer for vinyl chloride resin is used, vinylidene chloride resin rapidly undergoes dehydrochlorination reaction in about 10 minutes in the extrusion processing temperature range of 150 to 180 ° C., causing deterioration and black (See, for example, Patent Document 1 below). For this reason, processing of vinylidene chloride resin requires special equipment or special additives for processing.
ところで、本発明者は、本願と併行して出願した特許発明において、塩化ビニリデン樹脂に対して、軟質アクリル系樹脂及び所定の熱安定剤を含有させることにより、汎用の加工機器、通常の加工条件で長時間安定して加工可能な塩化ビニリデン樹脂組成物を提案した。しかしながら、その塩化ビニリデン樹脂組成物の物理的性質においては柔軟化の範囲に制約があり、また、加工条件においては加工温度にも制約があった。なお、塩化ビニリデン樹脂は、結晶性樹脂であるため、塩化ビニル樹脂あるいは他の結晶性樹脂とは単純に混合混錬しても均一に分散せず、このようなブレンド物の物理的性質は、非常に弱く且つ脆い特性がある。また、塩化ビニリデン樹脂は、塩化ビニル樹脂に比べて可塑剤の吸収性及び吸着量が劣っており、例えば、塩化ビニリデン樹脂１００重量部に対して１０から２０重量部程度しか吸着せず、これ以上の量を添加した場合、可塑剤が経時的に樹脂から噴き出すブリード現象が発生するという特性がある。軟質アクリル系樹脂は、塩化ビニリデン樹脂に均一に分散する一方、可塑剤の吸収性、吸着性に優れ、これらの特性は塩化ビニル樹脂並みである。しかしながら、可塑剤を過大に吸着させた場合、粘着力が強く且つ腰が弱くなってしまい、まともなシートにならない。 By the way, in the patented invention filed concurrently with the present application, the present inventor contains a soft acrylic resin and a predetermined heat stabilizer in a vinylidene chloride resin, thereby making it possible to process general-purpose processing equipment and general processing conditions. Proposed a vinylidene chloride resin composition that can be stably processed for a long time. However, in the physical properties of the vinylidene chloride resin composition, the range of softening is limited, and the processing temperature is also limited in processing conditions. In addition, since vinylidene chloride resin is a crystalline resin, it does not disperse uniformly even if it is simply mixed and kneaded with vinyl chloride resin or other crystalline resin, and the physical properties of such a blend are It has very weak and brittle properties. In addition, vinylidene chloride resin is inferior to vinyl chloride resin in absorbability and adsorption amount of plasticizer, and for example, it adsorbs only about 10 to 20 parts by weight with respect to 100 parts by weight of vinylidene chloride resin. When the amount of B is added, there is a characteristic that the bleeding phenomenon that the plasticizer spouts out of the resin with time occurs. The soft acrylic resin is dispersed uniformly in the vinylidene chloride resin, and is excellent in the absorbability and the adsorptivity of the plasticizer, and these properties are comparable to the vinyl chloride resin. However, when the plasticizer is excessively adsorbed, the adhesive strength is strong and the rigidity is weakened, and a sheet can not be formed properly.
以上のような事情に鑑み、本発明は、塩化ビニリデン樹脂が有する物理的特性である耐熱性、難燃性、耐薬品性等の性質、及び軟質アクリル樹脂の物理的特性である耐候性、耐寒性を保持するとともに、柔軟化の範囲、及び汎用加工設備での加工条件の範囲を拡大することを目的とする。 In view of the circumstances as described above, the present invention provides the physical properties of vinylidene chloride resin, such as heat resistance, flame retardancy, chemical resistance, etc., and the physical properties of soft acrylic resin, such as weather resistance, cold resistance The purpose is to maintain flexibility and expand the range of flexibility and the range of processing conditions in general-purpose processing equipment.
本発明者は、上記課題を見出し、上記課題を解決するために様々な工夫を試みた結果、塩化ビニリデン樹脂及び軟質アクリル系樹脂に対して、可塑剤を所定量含有させることにより、上記した柔軟化の範囲、加工温度等の制約を一挙に解放できることを見出し、本発明を完成させた。 The present inventors have found the above problems, and as a result of various attempts to solve the above problems, the above-mentioned softness can be obtained by containing a predetermined amount of plasticizer in vinylidene chloride resin and soft acrylic resin. The present invention has been completed by finding that restrictions such as the range of conversion, processing temperature, etc. can be released at once.
本発明の第１の態様によれば、塩化ビニリデン樹脂４０〜９７重量部、及び軟質アクリル系樹脂６０〜３重量部の合計１００重量部に対して、可塑剤１〜２７重量部を含む、塩化ビニリデン樹脂組成物が提供される。 According to the first aspect of the present invention, chloride is contained in an amount of 1 to 27 parts by weight based on 100 parts by weight of a total of 40 to 97 parts by weight of vinylidene chloride resin and 60 to 3 parts by weight of soft acrylic resin. Vinylidene resin compositions are provided.
本発明の第２の態様によれば、第１の態様において、さらに、塩化ビニリデン樹脂４０〜９７重量部及び軟質アクリル系樹脂６０〜３重量部の合計１００重量部に対して、ハイドロタルサイト系化合物及びゼオライト系化合物のうち少なくとも一方を含む熱安定剤０．３〜１０質量部を含む、塩化ビニリデン樹脂組成物が提供される。 According to the second aspect of the present invention, in the first aspect, the hydrotalcite-based resin is further added to 40 to 97 parts by weight of the vinylidene chloride resin and 60 to 3 parts by weight of the soft acrylic resin in total. A vinylidene chloride resin composition is provided which comprises 0.3 to 10 parts by mass of a heat stabilizer containing at least one of a compound and a zeolitic compound.
本発明の第３の態様によれば、第１又は第２の態様において、軟質アクリル系樹脂が、（メタ）アクリル酸メチルに由来する構成単位を含む非晶性樹脂である、塩化ビニリデン樹脂組成物が提供される。 According to a third aspect of the present invention, in the first or second aspect, the vinylidene chloride resin composition, wherein the soft acrylic resin is an amorphous resin containing a structural unit derived from methyl (meth) acrylate The goods are provided.
本発明の第４の態様によれば、第１から第３のいずれかの態様において、可塑剤が、フタル酸系エステル可塑剤、脂肪酸系エステル可塑剤、リン酸系エステル可塑剤、エポキシ系可塑剤、トリメリット酸系エステル可塑剤、ポリエステル系可塑剤、下記の特性を有する帯電防止可塑剤 、及び、安息香酸エステル系可塑剤からなる群から選択される少なくとも１種である、塩化ビニリデン樹脂組成物が提供される。
帯電防止可塑剤は、アジピン酸系エステル、フタル酸系エステル、及び第４級アンモニウム塩のうち少なくとも１種を含有する。
According to the fourth aspect of the present invention, in any of the first to third aspects, the plasticizer is a phthalic acid ester plasticizer, a fatty acid ester plasticizer, a phosphoric acid ester plasticizer, an epoxy resin Chloride resin composition which is at least one selected from the group consisting of a plasticizer, a trimellitic acid ester plasticizer, a polyester plasticizer, an antistatic plasticizer having the following characteristics, and a benzoic acid ester plasticizer The goods are provided.
The antistatic plasticizer contains at least one of an adipic acid ester, a phthalic acid ester, and a quaternary ammonium salt.
本発明の第５の態様によれば、第１から第４のいずれかの態様において、塩化ビニリデン樹脂は、一度も成形加工されていない未使用樹脂、成形加工された樹脂廃材、又は未使用樹脂と樹脂廃材との混合物のいずれかである、塩化ビニリデン樹脂組成物が提供される。 According to the fifth aspect of the present invention, in any of the first to fourth aspects, the vinylidene chloride resin is a virgin resin that has never been molded, a resin waste material that has been molded, or a virgin resin A vinylidene chloride resin composition is provided, which is any one of a mixture of the above and a resin waste.
本発明の第６の態様によれば、第１から第５のいずれかの態様の塩化ビニリデン樹脂組成物、及び塩化ビニリデン樹脂組成物以外の樹脂を含む樹脂ブレンド物であって、塩化ビニリデン樹脂組成物を１５重量％以上含む、樹脂ブレンド物が提供される。 According to a sixth aspect of the present invention, there is provided a vinylidene chloride resin composition according to any one of the first to fifth aspects, and a resin blend containing a resin other than the vinylidene chloride resin composition, wherein the vinylidene chloride resin composition The present invention provides a resin blend containing 15% by weight or more of
本発明の塩化ビニリデン樹脂組成物は、塩化ビニリデン樹脂が有する物理的特性である耐熱性、難燃性、耐薬品性等の性質、及び軟質アクリル樹脂の物理的特性である耐候性、耐寒性を保持するとともに、柔軟化の範囲及び汎用加工設備での加工条件の範囲を拡大することができる。 The vinylidene chloride resin composition of the present invention has the physical properties of vinylidene chloride resin, such as heat resistance, flame retardancy and chemical resistance, and the physical properties of soft acrylic resin, such as weather resistance and cold resistance. While maintaining it, the range of flexibility and the range of processing conditions in general purpose processing equipment can be expanded.
以下、本発明の実施形態について説明する。ただし、本発明は以下に説明する実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described below.
実施形態に係る塩化ビニリデン樹脂組成物（以下、「樹脂組成物」と称す。）は、所定の塩化ビニリデン樹脂及び軟質アクリル系樹脂の合計１００重量部に対して、所定の可塑剤を含有する。 The vinylidene chloride resin composition (hereinafter referred to as "resin composition") according to the embodiment contains a predetermined plasticizer with respect to a total of 100 parts by weight of the predetermined vinylidene chloride resin and the soft acrylic resin.
塩化ビニリデン樹脂は、塩化ビニリデン樹脂全体に対して、塩化ビニリデンに由来する構成単位を５０重量％以上含む樹脂をいう。塩化ビニリデン樹脂は、例えば、塩化ビニリデン単独重合体、塩化ビニリデンと他の単量体との共重合体、及びこれらの混合物を含むことができる。また、塩化ビニリデン樹脂は、他の樹脂や少量の添加剤を含んでもよい。 The vinylidene chloride resin refers to a resin containing 50% by weight or more of a constitutional unit derived from vinylidene chloride with respect to the entire vinylidene chloride resin. The vinylidene chloride resin can include, for example, a vinylidene chloride homopolymer, a copolymer of vinylidene chloride and another monomer, and a mixture thereof. The vinylidene chloride resin may also contain other resins and small amounts of additives.
塩化ビニリデン樹脂は、他の単量体との共重合体を用いる場合、他の単量体としては、塩化ビニリデン（樹脂）と共重合可能なものであれば、任意のものを用いることができる。他の単量体としては、例えば、塩化ビニル、（メタ）アクリル酸エステル、酢酸ビニル、アクリロニトリル等が挙げられ、これらは１種を単独で用いてもよいし、２種以上を併用してもよい。塩化ビニリデンと他の単量体との共重合体としては、例えば、塩化ビニリデン−塩化ビニル共重合体、塩化ビニリデン−（メタ）アクリル酸エステル共重合体、塩化ビニリデン−酢酸ビニル共重合体等が挙げられ、これらは１種を単独で用いてもよいし、２種以上を併用してもよい。なお、本明細書において（メタ）アクリル酸とは、アクリル酸及び／又はメタクリル酸を意味し、例えば、（メタ）アクリル酸エステルとは、アクリル酸エステル及び／又はメタクリル酸エステルを意味する。 When a copolymer with other monomers is used as the vinylidene chloride resin, any other monomer can be used as long as it is copolymerizable with vinylidene chloride (resin). . Examples of other monomers include vinyl chloride, (meth) acrylic acid ester, vinyl acetate, acrylonitrile and the like, and one of these may be used alone, or two or more may be used in combination. Good. As a copolymer of vinylidene chloride and another monomer, for example, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride- (meth) acrylate copolymer, vinylidene chloride-vinyl acetate copolymer, etc. These may be used alone or in combination of two or more. In the present specification, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and for example, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester.
塩化ビニリデン樹脂は、一度も成形加工されていない未使用樹脂（バージン材）、成形加工された樹脂廃材及びこれらの混合物を用いることができる。塩化ビニリデン樹脂が樹脂廃材を含有する場合、製造コストを下げることができるとともに環境負荷を軽減することができる。また、塩化ビニリデン樹脂は、樹脂廃材のみからなるものでもよい。樹脂廃材としては、廃材であれば、任意のものを用いることができ、複数の物質が混在してもよい。これらの中でも、ラップ、シート、フィルム等の製造時に発生した樹脂廃材を用いることが好ましい。このような製造時に発生した樹脂廃材を用いる場合、不純物の混入が少ないため、高品質の樹脂組成物を製造することができる。 As vinylidene chloride resin, virgin resin (virgin material) which has never been molded and processed, resin molded material which has been molded and processed, and a mixture thereof can be used. When the vinylidene chloride resin contains resin waste material, the manufacturing cost can be reduced and the environmental load can be reduced. Further, the vinylidene chloride resin may be made only of resin waste material. As the resin waste material, any waste material can be used, and a plurality of substances may be mixed. Among these, it is preferable to use the resin waste material generated at the time of manufacturing a wrap, a sheet, a film and the like. In the case of using the resin waste material generated at the time of such production, high-quality resin composition can be produced because mixing of impurities is small.
樹脂組成物は、所定の軟質アクリル系樹脂を含有する。軟質アクリル系樹脂は、軟質のアクリル系樹脂である。軟質アクリル系樹脂は、上記したように本発明者が上記課題の解決等のために様々な樹脂を検討した中で、見出されて採用された樹脂であり、塩化ビニリデン樹脂に対する分散性に優れ、塩化ビニリデン樹脂の特性を保ちつつ、軟質アクリル系樹脂の特性を付与することができ、さらに、特異な熱安定性を付与することができる。中でも、軟質アクリル系樹脂は、例えば、（メタ）アクリル酸メチルに由来する構成単位を含む非晶性樹脂であるのが好ましく、軟質アクリル系樹脂が、メタクリル酸メチルとアクリル酸メチルとの共重合体をベースに、（メタ）アクリル酸ブチル、更に（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２エチルヘキシル等の（メタ）アクリル酸系エステル、あるいはスチレンなどを付与した共重合体であるのがより好ましい。 The resin composition contains a predetermined soft acrylic resin. The soft acrylic resin is a soft acrylic resin. The soft acrylic resin is a resin found and adopted while the present inventors examined various resins for solving the above problems as described above, and it is excellent in dispersibility to vinylidene chloride resin. The characteristics of the soft acrylic resin can be imparted while maintaining the characteristics of the vinylidene chloride resin, and further, unique thermal stability can be imparted. Among them, the soft acrylic resin is preferably, for example, an amorphous resin containing a structural unit derived from methyl (meth) acrylate, and the soft acrylic resin is a copolymer of methyl methacrylate and methyl acrylate. Copolymers obtained by adding butyl (meth) acrylate, and further (meth) acrylic acid esters such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or styrene based on the united substance More preferable.
また、軟質アクリル系樹脂は、例えば、メタクリル酸エステル及び／又はアクリル酸エステルと、スチレンとの共重合体を含む樹脂であって、軟質樹脂成分と、硬質樹脂成分とを混合してなるものでもよい。軟質樹脂成分は、例えば、弾性率１〜１０ＭＰａ、好ましくは３〜８ＭＰａを有する、炭素数５〜１３のメタクリル酸エステル及び／又は炭素数４〜１２のアクリル酸エステルと、スチレンとの共重合体である。例えば、軟質アクリル系樹脂は、炭素数５〜１３のメタクリル酸アルキルエステル５５〜８５質量部及び／又は炭素数４〜１２のアクリル酸アルキルエステル１０〜３５質量部と、スチレン５〜２５質量部との共重合体が挙げられ、上記アルキル基としては、メチル、エチル、プロピル、ブチル、２−エチルヘキシル基等を挙げることができる。また、軟質アクリル系樹脂は、例えば、ＩＳＯ４８に準じて測定した硬度が、Ａ６０〜Ａ９０であるのが好ましい。例えば、軟質アクリル系樹脂は、市販品のクラレ社製、商品名パラペットＳＡシリーズを用いてもよい。 Also, the soft acrylic resin is, for example, a resin containing a copolymer of methacrylic acid ester and / or acrylic acid ester and styrene, which is formed by mixing a soft resin component and a hard resin component. Good. The soft resin component is, for example, a copolymer of styrene with a methacrylic acid ester of 5 to 13 carbon atoms and / or an acrylic ester of 4 to 12 carbon atoms, and having an elastic modulus of 1 to 10 MPa, preferably 3 to 8 MPa. It is. For example, the soft acrylic resin comprises 55 to 85 parts by mass of methacrylic acid alkyl ester having 5 to 13 carbon atoms and / or 10 to 35 parts by mass of acrylic acid alkyl ester having 4 to 12 carbon atoms and 5 to 25 parts by mass of styrene And the above alkyl group includes methyl, ethyl, propyl, butyl, 2-ethylhexyl group and the like. Moreover, as for soft acrylic resin, it is preferable that the hardness measured according to ISO48 is A60-A90, for example. For example, as the soft acrylic resin, commercially available product Kuraray Co., Ltd., trade name Parapet SA series may be used.
軟質アクリル系樹脂は、塩化ビニリデン樹脂４０〜９７重量部に対して、６０〜３重量部含有される。軟質アクリル系樹脂は、好ましくは、塩化ビニリデン樹脂５０〜９７重量部に対して、５０〜３重量部含有される。なお、軟質アクリル系樹脂と塩化ビニリデン樹脂との合計は、１００重量部に設定される。上記の塩化ビニリデン樹脂に対する軟質アクリル系樹脂の割合は、製造する樹脂組成物の特性に応じて、適宜、設定される。例えば、塩化ビニリデン樹脂に対する軟質アクリル系樹脂の割合を多くすれば、軟質アクリル系樹脂の特性、例えば柔軟性、耐候性等を、より多く付与することができる。例えば、樹脂組成物により多く耐候性を付与する場合、塩化ビニリデン樹脂及び軟質アクリル系樹脂の合計１００重量部に対して、軟質アクリル系樹脂を１５重量部以上が好ましく、２０重量部以上がより好ましい。 The soft acrylic resin is contained in an amount of 60 to 3 parts by weight with respect to 40 to 97 parts by weight of the vinylidene chloride resin. The soft acrylic resin is preferably contained in an amount of 50 to 3 parts by weight based on 50 to 97 parts by weight of the vinylidene chloride resin. The total of the soft acrylic resin and the vinylidene chloride resin is set to 100 parts by weight. The ratio of the soft acrylic resin to the vinylidene chloride resin is appropriately set according to the characteristics of the resin composition to be produced. For example, if the ratio of the soft acrylic resin to the vinylidene chloride resin is increased, it is possible to impart more properties of the soft acrylic resin, such as flexibility, weatherability, and the like. For example, in the case of imparting more weather resistance to the resin composition, 15 parts by weight or more of the soft acrylic resin is preferable, and 20 parts by weight or more is more preferable based on 100 parts by weight in total of vinylidene chloride resin and soft acrylic resin. .
樹脂組成物は、可塑剤を所定量で含有する。可塑剤は、柔軟性、あるいは対候性等を改質する物質である。また、本実施形態において可塑剤は、上記したように本発明者が上記課題の解決等のために様々な樹脂を検討した中で、見出されて採用されたものであり、塩化ビニリデン樹脂及び軟質アクリル樹脂の特性を損ねずに、熱安定性を特異に向上させる。本実施形態では、樹脂組成物が、軟質アクリル樹脂及び可塑剤を、特定量含有させることにより、塩化ビニリデン樹脂及び軟質アクリル樹脂の特性を損ねずに、熱安定性を特異に向上させると推察される。可塑剤は、例えば、ポリ塩化ビニル樹脂用の可塑剤として、通常用いられる可塑剤を用いることができる。中でも、可塑剤は、フタル酸系エステル可塑剤、脂肪酸エステル可塑剤、燐酸エステル系可塑剤、エポキシ系可塑剤、及びトリメリット酸系エステル可塑剤、ポリエステル系可塑剤、帯電防止可塑剤、及び、安息香酸エステル系可塑剤からなる群より選ばれる少なくとも１種であるのが、熱安定性を向上させる観点から好ましく、中でも、フタル酸系エステル系可塑剤及びエポキシ系可塑剤からなる群より選ばれる少なくとも１種であるのがより好ましい。なお、上記帯電防止可塑剤は、アジピン酸系エステル、フタル酸系エステル、及び第４級アンモニウム塩のうち少なくとも１種を含有する。このような可塑剤としては、例えば、ジ−２−エチルヘキシルフタレート（ＤＯＰ）、ジブチルフタレート（ＤＢＰ）、ジヘプチルフタレート（ＤＨＰ）、ジイソデシルフタレート（ＤＩＤＰ）等のフタル酸系エステル可塑剤；ジ−２−エチルヘキシルアジペート（ＤＯＡ）、ジイソブチルアジペート（ＤＩＢＡ）、ジブチルアジペート（ＤＢＡ）等の脂肪酸エステル系可塑剤；トリメチルホスフェート（ＴＭＰ）、トリエチルホスフェート（ＴＥＰ）等の燐酸エステル系可塑剤；エポキシ化大豆油のようなエポキシ化植物脂等のエポキシ系可塑剤；トリー２−エチルヘキシルトリメリテート（ＴＯＴＭ）、トリイソノニルトリメリテート（ＴＩＮＴＭ）等のトリメリット酸系エステル可塑剤；アジピン酸系ポリエステル、セバチン酸系ポリエステル、トリメリット酸系ポリエステル、ピロメリット酸系ポリエステル等のポリエステル系可塑剤；アジピン酸系エステルを有する株式会社ＡＤＥＫＡ社製：商品名「アデカサイザーＬＶ−８０８」、フタル酸系エステルを有する株式会社ＡＤＥＫＡ社製：商品名「アデカサイザーＬＶ−８４８」、第４級アンモニウム塩を有する株式会社ＡＤＥＫＡ社製：商品名「アデカサイザーＬＶ−７０」等の帯電防止可塑剤、及び、エチレングリコール安息香酸エステル、ジエチレングリコールジ安息香酸エステル、トリエチレングリコールジ安息香酸エステル、ポリエチレングリコールジ安息香酸エステル、プロピレングリコールジ安息香酸エステル等の安息香酸エステル系可塑剤；などが挙げられる。可塑剤が帯電防止可塑剤を含有する場合、帯電を抑制することができる。 The resin composition contains a plasticizer in a predetermined amount. The plasticizer is a substance that modifies flexibility, weatherability, and the like. Further, in the present embodiment, as described above, the plasticizer was found and adopted while the present inventors examined various resins for the purpose of solving the above-mentioned problems, etc. The heat stability is uniquely improved without losing the properties of the soft acrylic resin. In the present embodiment, it is surmised that the resin composition specifically improves the thermal stability by containing the soft acrylic resin and the plasticizer in specific amounts without impairing the characteristics of the vinylidene chloride resin and the soft acrylic resin. Ru. As the plasticizer, for example, a plasticizer that is usually used can be used as a plasticizer for polyvinyl chloride resin. Among them, phthalate ester plasticizers, fatty acid ester plasticizers, phosphate ester plasticizers, epoxy plasticizers, trimellitic acid ester plasticizers, polyester plasticizers, antistatic plasticizers, and It is preferable from the viewpoint of improving the thermal stability that at least one selected from the group consisting of benzoic acid ester plasticizers is selected from among the group consisting of phthalic acid ester plasticizers and epoxy plasticizers. More preferably, it is at least one. The antistatic plasticizer contains at least one of an adipic acid ester, a phthalic acid ester, and a quaternary ammonium salt. Examples of such plasticizers include phthalic acid based ester plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and diisodecyl phthalate (DIDP); -Fatty acid ester based plasticizers such as ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA); phosphoric acid based plasticizers such as trimethyl phosphate (TMP), triethyl phosphate (TEP); Epoxidized soybean oil Epoxy plasticizers such as epoxidized vegetable fat; trimellitic acid ester plasticizers such as tri 2-ethylhexyl trimellitate (TOTM), triisononyl trimellitate (TINTM); adipic acid polyester, sebacic acid Poly Polyester plasticizers such as Stel, trimellitic acid polyester, pyromellitic acid polyester; ADEPA Co., Ltd. having an adipic acid ester: manufactured by ADEKA Co., Ltd .: trade name "Adekasizer LV-808", phthalic acid ester Made by Adeka: trade name "Adecasizer LV-848", manufactured by ADEKA Co., Ltd. having quaternary ammonium salt: antistatic plasticizer such as trade name "Adecasizer LV-70", and ethylene glycol benzoate And benzoic acid ester plasticizers such as diethylene glycol dibenzoic acid ester, triethylene glycol dibenzoic acid ester, polyethylene glycol dibenzoic acid ester, and propylene glycol dibenzoic acid ester. When the plasticizer contains an antistatic plasticizer, charging can be suppressed.
樹脂組成物は、上記の塩化ビニリデン樹脂及び軟質アクリル系樹脂の合計１００重量部に対して、可塑剤を１〜２７重量部を含有する。中でも、可塑剤は、上記の塩化ビニリデン樹脂及び軟質アクリル系樹脂の合計１００重量部に対して、１〜２０重量部含有させるのが好ましい。樹脂組成物が可塑剤を上記の範囲で含有する場合、塩化ビニリデン樹脂が有する物理的特性である耐熱性、難燃性、耐薬品性等の性質、及び軟質アクリル樹脂の物理的特性である耐候性、耐寒性を保持するとともに、柔軟化の範囲及び汎用加工設備での加工条件の範囲を拡大することができ、表面性（成形加工性）が良好で、樹脂のブロッキングも抑制される。なお、可塑剤の含有量が上記範囲から外れる場合、例えば、可塑剤の含有量が上記の塩化ビニリデン樹脂及び軟質アクリル系樹脂の合計１００重量部に対して２７重量部を超える場合、ブロッキングが顕著になり合紙（挿間紙）が必要になり、また、５０重量部を超えると、上記のブロッキングに加えて、成形加工時にロールから取り出すときにドローダウンが生じ易くなるなど樹脂組成物の加工が困難になる。 The resin composition contains 1 to 27 parts by weight of a plasticizer with respect to a total of 100 parts by weight of the vinylidene chloride resin and the soft acrylic resin. Among them, the plasticizer is preferably contained in an amount of 1 to 20 parts by weight with respect to 100 parts by weight in total of the vinylidene chloride resin and the soft acrylic resin. When the resin composition contains a plasticizer in the above range, the physical properties of the vinylidene chloride resin, such as heat resistance, flame retardancy, chemical resistance, etc., and the physical properties of the soft acrylic resin, weather resistance While maintaining the properties and cold resistance, the range of softening and the range of processing conditions in general-purpose processing equipment can be expanded, the surface property (molding processability) is good, and blocking of the resin is also suppressed. In addition, when the content of the plasticizer is out of the above range, for example, when the content of the plasticizer exceeds 27 parts by weight with respect to 100 parts by weight in total of the vinylidene chloride resin and the soft acrylic resin, the blocking is remarkable. And an interleaf paper (inserted intercalated paper) is required, and if it exceeds 50 parts by weight, in addition to the above blocking, drawdown tends to occur when taking it out of the roll during molding processing, etc. Will be difficult.
樹脂組成物は、ハイドロタルサイト系化合物及びゼオライトのうち少なくとも一方を含む熱安定剤を含有するのが好ましい。樹脂組成物が熱安定剤を含有する場合、より熱安定性を向上させることができ、汎用加工設備での加工条件の範囲を拡大することができる。 The resin composition preferably contains a heat stabilizer containing at least one of a hydrotalcite compound and a zeolite. When the resin composition contains a heat stabilizer, the heat stability can be further improved, and the range of processing conditions in a general-purpose processing facility can be expanded.
ハイドロタルサイト系化合物は、熱安定性を向上させる。ハイドロタルサイト系化合物は、上記した塩化ビニリデン樹脂の熱安定性を向上させるのに好ましい熱安定剤である。ハイドロタルサイト系化合物は、２価の金属イオンと３価の金属イオンからなる層状複水酸化物であって、層間に陰イオンを持つ化合物である。例えば、ハイドロタルサイト系化合物は、下記一般式（１）で表される化合物を用いることができ、これらは１種を単独で用いてもよいし、２種以上を併用してもよい。
Ｍ２＋ １―ＸＭ３＋ Ｘ（ＯＨ）２（Ａｎ−）Ｘ／ｎ・ｍＨ２Ｏ・・・（１）
The hydrotalcite compound improves the thermal stability. Hydrotalcite compounds are preferred heat stabilizers to improve the thermal stability of the vinylidene chloride resin described above. The hydrotalcite-based compound is a layered double hydroxide composed of a divalent metal ion and a trivalent metal ion, and is a compound having an anion between layers. For example, as the hydrotalcite compound, a compound represented by the following general formula (1) can be used, and one of these may be used alone, or two or more may be used in combination.
M 2+ 1−X M 3+ X (OH) 2 (A n− ) X / n · mH 2 O (1)
一般式（１）中、Ｍ２＋は、２価の金属イオンであり、Ｍ３＋は、３価の金属イオンであり、Ａｎ−はｎ価アニオンである。また、ｘは、０＜ｘ＜０．５の条件を満足する数値であり、ｍは、０≦ｍ≦４の条件を満足する数値である。 In general formula (1), M 2+ is a divalent metal ion, M 3+ is a trivalent metal ion, and An- is an n-valent anion. Further, x is a numerical value satisfying the condition of 0 <x <0.5, and m is a numerical value satisfying the condition of 0 ≦ m ≦ 4.
Ｍ２＋としては、マグネシウム（Ｍｇ２＋）、コバルト（Ｃｏ２＋）、ニッケル（Ｎｉ２＋）、亜鉛（Ｚｎ２＋）等が挙げられ、中でもＭｇ２＋が好ましい。Ｍ３＋としては、例えば、アルミニウム（Ａｌ３＋）、コバルト（Ｃｏ３＋）、鉄（Ｆｅ３＋）、クロム（Ｃｒ３＋）等が挙げられ、中でもＡｌ３＋が好ましい。Ａｎ−としては、例えば、Ｃｌ−、Ｂｒ−、Ｉ−、ＮＯ２ −、ＣｌＯ４ −、ＳＯ４ ２−、ＣＯ３ ２−、ＳｉＯ３ ２−、Ｓｉ２Ｏ５ ２−、ＨＰＯ４ ２−、ＨＢＯ３ ２−、ＰＯ４ ３−、Ｆｅ（ＣＮ）６ ３−、Ｆｅ（ＣＮ）４ ４−、ＣＨ３ＣＯＯ−、Ｃ６Ｈ４（ＯＨ）ＣＯＯ−、（ＯＣＯＣＯＯ）２−、（ＯＣＯＣ６Ｈ４ＣＯＯ）２−等が挙げられ、中でもＣＯ３ ２−が好ましい。 Examples of M 2 + include magnesium (Mg 2 + ), cobalt (Co 2 + ), nickel (Ni 2 + ), zinc (Zn 2 + ) and the like, and among these, Mg 2 + is preferable. Examples of M 3+ include aluminum (Al 3+ ), cobalt (Co 3+ ), iron (Fe 3+ ), chromium (Cr 3+ ) and the like, and among these, Al 3+ is preferable. The A n-, for example, Cl -, Br -, I -, NO 2 -, ClO 4 -, SO 4 2-, CO 3 2-, SiO 3 2-, Si 2 O 5 2-, HPO 4 2 − , HBO 3 2− , PO 4 3− , Fe (CN) 6 3− , Fe (CN) 4 4− , CH 3 COO − , C 6 H 4 (OH) COO − , (OCOCOO) 2− , ( OCOC 6 H 4 COO) 2- etc., and among them, CO 3 2- is preferable.
上記ハイドロタルサイト系化合物の中でも、熱安定性の向上、入手容易性の観点から、一般式：Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ（一般式（１）中、ｘ＝０．２５、ｎ＝２、ｍ＝０．５）で表される化合物が好ましい。 Among the above hydrotalcite compounds, from the viewpoint of improvement in thermal stability and availability, the general formula: Mg 6 Al 2 (OH) 16 CO 3 · 4H 2 O (in the general formula (1), x = 0 The compound represented by .25, n = 2, m = 0.5) is preferable.
ハイドロタルサイト系化合物は、天然鉱物（ハイドロタルク石、あるいはマナセアイト）、合成物及びこれらの混合物を用いることができる。合成物を用いる場合、不純物の含有がより少ないものとなる。天然鉱物としては、また、ハイドロタルサイト系化合物は、市販品を用いることができる。市販品としては、例えば、大協化成工業株式会社製の商品名ＲＸ３０４Ｂ（一般式：Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ）等を用いることができる。ハイドロタルサイト系化合物の粒子径は、限定されないが、平均粒子径で１μｍ以下のものを用いる場合、樹脂組成物中に容易に分散させることができ、その結果、熱安定性がより効果的に向上する。 As the hydrotalcite-based compound, natural minerals (hydrotalcite or manaceite), synthetic products, and mixtures thereof can be used. When a compound is used, the content of impurities is less. As a natural mineral, a hydrotalcite type compound can also use a commercial item. As a commercial item, for example, trade name RX304B (general formula: Mg 6 Al 2 (OH) 16 CO 3 · 4H 2 O) manufactured by Daikyo Kasei Kogyo Co., Ltd. can be used. The particle size of the hydrotalcite compound is not limited, but when using one having an average particle size of 1 μm or less, it can be easily dispersed in the resin composition, and as a result, the thermal stability is more effective. improves.
ゼオライトは、熱安定性を向上させる。ゼオライトは、特開２０１６−２０４５３７号公報、及び特開２０１６−２０４５３８号公報に記載するように、上記のハイドロタルサイト系化合物に代えて、あるいは上記のハイドロタルサイト系化合物とともに用いることができ、上記した塩化ビニリデン樹脂の熱安定性を向上させるのに好ましい熱安定剤である。ゼオライトは、アルミノケイ酸塩からなり、その結晶構造中に空隙を有する。ゼオライトは、例えば、アルミノケイ酸ナトリウムを主成分とするものを用いることができ、１種を単独又は２種以上を併用して用いることができる。また、ゼオライトは、天然物及び合成物のいずれも用いることができる。ゼオライトは、合成物を用いる場合、不純物の含有が少ないので好ましい。また、ゼオライトは、市販品を用いることができる。市販品としては、例えば、大協化成工業株式会社製の商品名ＲＸ３０４Ａ（アルミノケイ酸塩が主成分である合成物）等を用いることができる。ゼオライトの粒子径は、特に限定されないが、例えば、平均粒子径で１μｍ以下のものを用いる場合、樹脂組成物中に容易に分散させることができ、より効果的に樹脂組成物の熱安定性を向上させることができる。 Zeolites improve thermal stability. Zeolites can be used in place of the above hydrotalcite compounds or together with the above hydrotalcite compounds as described in JP-A-2016-204537 and JP-A-2016-204538. It is a preferable heat stabilizer to improve the thermal stability of the above-mentioned vinylidene chloride resin. Zeolite consists of an aluminosilicate and has voids in its crystal structure. As the zeolite, for example, one having sodium aluminosilicate as a main component can be used, and one species can be used alone or two or more species can be used in combination. In addition, as the zeolite, both natural products and synthetic products can be used. Zeolites are preferred when using a synthetic product because they contain less impurities. Moreover, a commercial item can be used for zeolite. As a commercial item, for example, a trade name RX304A (a synthetic product mainly composed of an aluminosilicate) manufactured by Daikyo Kasei Kogyo Co., Ltd. can be used. The particle size of the zeolite is not particularly limited. For example, when using an average particle size of 1 μm or less, the zeolite can be easily dispersed in the resin composition, and the thermal stability of the resin composition can be more effectively achieved. It can be improved.
熱安定剤は、塩化ビニリデン樹脂４０〜９７重量部及び軟質アクリル系樹脂６０〜３重量部の合計１００重量部に対して、好ましくは０．３〜１０重量部、より好ましくは０．５〜１０重量部含有される。熱安定剤の含有量が上記範囲である場合、熱安定性が向上する。熱安定剤は、塩化ビニリデン樹脂１００重量部に対して、０．３重量部未満では、効果が十分ではなく、また、１０重量部を超えて添加しても効果は変わらない。 The heat stabilizer is preferably 0.3 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of 40 to 97 parts by weight of vinylidene chloride resin and 60 to 3 parts by weight of soft acrylic resin. It is contained by weight. When the content of the heat stabilizer is in the above range, the heat stability is improved. If the heat stabilizer is less than 0.3 parts by weight with respect to 100 parts by weight of the vinylidene chloride resin, the effect is not sufficient, and addition of more than 10 parts by weight does not change the effect.
また、本実施形態の樹脂組成物は、添加剤などの他の成分を含んでもよい。添加剤は、特に限定されないが、例えば、酸化防止剤、金属石鹸類、強化剤、スリップ剤、帯電防止剤、顔料、無機及び有機の充填剤等を用いることができる。添加剤の含有量は、本発明の趣旨を逸脱しない量であれば、任意である。例えば、酸化防止剤としては、フェノール系酸化防止剤を用いることができる。なお、フェノール系酸化防止剤は、アデカスタブＡＯシリーズ（アデカ社製）等の市販品を用いてもよい。フェノール系酸化防止剤は、例えば、塩化ビニリデン樹脂及び軟質アクリル系樹脂を合わせた１００重量部に対して、０．１〜０．４重量部含有されるのが好ましい。 Moreover, the resin composition of this embodiment may also contain other components, such as an additive. The additive is not particularly limited, and, for example, an antioxidant, metal soaps, a reinforcing agent, a slip agent, an antistatic agent, a pigment, an inorganic and organic filler, and the like can be used. The content of the additive is arbitrary as long as it does not deviate from the purpose of the present invention. For example, a phenolic antioxidant can be used as the antioxidant. In addition, you may use commercial items, such as Adekastab AO series (made by Adeka), as a phenolic antioxidant. The phenolic antioxidant is preferably contained in an amount of 0.1 to 0.4 parts by weight, for example, based on 100 parts by weight of the total of vinylidene chloride resin and soft acrylic resin.
さらに、樹脂組成物は、他樹脂と混合混錬してブレンド物を作る場合も有効である。すなわち、本実施形態の樹脂組成物及び樹脂組成物以外の樹脂を含む、樹脂ブレンド物であってもよい。例えば、樹脂ブレンド物は、例えば、本実施形態の樹脂組成物を１５％以上含み、２０％以上を含むのが好ましい。樹脂ブレンド物は、例えば、樹脂組成物を２０％以上３０％以下含んでもよい。樹脂ブレンド物は、樹脂組成物を上記範囲で含む場合、樹脂組成物の特性を付与することができ、例えば、本実施形態の本実施形態の樹脂組成物を５０％以上含む場合、本実施形態の樹脂組成物の効果（特性）が顕著になる。 Furthermore, the resin composition is also effective when mixed with other resins to form a blend. That is, it may be a resin blend containing a resin other than the resin composition of the present embodiment and the resin composition. For example, the resin blend preferably contains, for example, 15% or more and 20% or more of the resin composition of the present embodiment. The resin blend may contain, for example, 20% or more and 30% or less of the resin composition. When the resin blend contains the resin composition in the above range, it can impart the characteristics of the resin composition. For example, when the resin composition of the present embodiment of the present embodiment contains 50% or more, the present embodiment The effect (characteristics) of the resin composition of
樹脂組成物は、通常の混合装置、例えばヘンシェルミキサー（商品名）、スーパーミキサー（商品名）、リボンブレンダー等を用いて混合し、直接又は押出し機等で造粒後、射出成型法、押出し成形法、ブロー成型法、プレス成型法、カレンダー成形法などにより目的とする成形品の製造に供される。詳細については、後に説明する。 The resin composition is mixed using a conventional mixing apparatus such as Henschel mixer (trade name), Super mixer (trade name), ribbon blender, etc. and granulated directly or by an extruder etc., followed by injection molding, extrusion molding It is used for the manufacture of the target molded article by a method, a blow molding method, a press molding method, a calendar molding method, etc. Details will be described later.
上記のように、本実施形態の樹脂組成物は、塩化ビニリデン樹脂４０〜９７重量部、及び軟質アクリル系樹脂６０〜３重量部の合計１００重量部に対して、可塑剤１〜２７重量部を含む。この構成により、本実施形態の樹脂組成物は、塩化ビニリデン樹脂が有する物理的特性である耐熱性、難燃性、耐薬品性等の性質、及び軟質アクリル樹脂の物理的特性である耐候性、耐寒性を保持するとともに、柔軟化の範囲及び汎用加工設備での加工条件の範囲を拡大することができる。例えば、本発明の塩化ビニリデン樹脂組成物、及び樹脂ブレンド物は、塩化ビニリデン樹脂の機能的特性である耐熱性、ガスバリヤー性、難燃性、耐薬品性を有し、且つ、加工性（成形性、成膜性）に優れ、加工温度の範囲が１３０〜１５０℃の広い範囲で長時間、安定して加工生産が可能であり、特殊な設備、材料及び方法を必要とすることなく、容易に製造することができる。例えば、本実施形態の樹脂組成物は、ＵＬ９４燃焼試験において、Ｖ−０、Ｖ−１、Ｖ−２の難燃性を有する。また、例えば、本実施形態の樹脂組成物は、ＪＩＳ Ｋ ７２０６に基づく硬度が５５〜９５の広い範囲に任意に設定可能であり、柔軟化の範囲が広く、柔軟性が必要とされる幅広い製品にも適用可能である。また、本発明の樹脂組成物は、特別高価な化合物を含んでいないので、比較的安価であり、経済性、実用性に優れている。 As described above, the resin composition of the present embodiment contains 1 to 27 parts by weight of a plasticizer with respect to a total of 100 parts by weight of 40 to 97 parts by weight of a vinylidene chloride resin and 60 to 3 parts by weight of a soft acrylic resin. Including. With this configuration, the resin composition of the present embodiment has the physical properties of vinylidene chloride resin, such as heat resistance, flame retardancy and chemical resistance, and the physical properties of soft acrylic resin, such as weather resistance, While maintaining cold resistance, the range of flexibility and the range of processing conditions in a general-purpose processing facility can be expanded. For example, the vinylidene chloride resin composition and resin blend of the present invention have heat resistance, gas barrier property, flame retardancy, chemical resistance, which are functional characteristics of vinylidene chloride resin, and processability (molding And film forming properties, and stable processing and production is possible for a long time in a wide range of processing temperatures from 130 to 150 ° C., and it is easy without requiring special equipment, materials and methods. Can be manufactured. For example, the resin composition of the present embodiment has flame retardancy of V-0, V-1, and V-2 in the UL94 combustion test. Also, for example, the resin composition of the present embodiment can be arbitrarily set in a wide range of hardness from 55 to 95 based on JIS K 7206, a wide range of flexibility, and a wide range of products requiring flexibility. Is also applicable. In addition, the resin composition of the present invention is relatively inexpensive and is excellent in economy and practicability because it does not contain a particularly expensive compound.
次に、実施形態に係る成形体を説明する。成形体は、上記した本実施形態の樹脂組成物を用いて形成され、上記した塩化ビニリデン樹脂の機能的特性である耐熱性、ガスバリヤー性、難燃性、耐薬品性を保ちつつ、軟質アクリル系樹脂の機能的特性である、熱安定性、耐候性、耐寒性、加工性、表面性、及び物理的性質を有し、さらに、硬度が５５〜９５の広い範囲に任意に設定可能であり、柔軟性が必要とされる幅広い製品にも適用可能である。また、成形体は、上記したように、加工温度の範囲が１３０〜１５０℃の広い範囲で長時間、安定して加工生産が可能であり、特殊な設備、材料及び方法を必要とすることなく、容易に製造することができる。例えば、成形体は、成形加工性に優れるため、カレンダー成形法、射出成形法、押出し成形法、ブロー成形法、プレス成形法等の公知の汎用加工法により容易に製造することができる。また、成形体は、上記した樹脂廃材を使用して製造する場合、低コストで製造することができる。成形体としては、例えば、建材、土木資材、農業用資材、包装資材などに用いるシートやフィルム、繊維材料等に用いることができる。中でも、成形体は、上記したように、熱安定性、耐候性、耐寒性、難燃性、耐薬品性などに優れるため、建材、土木資材、農業用資材、包装資材など室外の用途に好適に用いることができる。以上のように、本実施形態に係る成形体は、上記の優れた特性を有するため、幅広い用途に用いることができ、産業的利用価値が高い。なお、成形体は、上記の本実施形態の樹脂組成物を含む樹脂ブレンド物を用いて形成されてもよい。 Next, a molded body according to the embodiment will be described. A molded article is formed using the resin composition of the above-described embodiment, and maintains the heat resistance, gas barrier property, flame retardancy, chemical resistance, which are the functional characteristics of the above-mentioned vinylidene chloride resin, and soft acrylic. It has thermal stability, weather resistance, cold resistance, processability, and physical properties, which are functional properties of the resin based resin, and further, hardness can be arbitrarily set in a wide range of 55 to 95. It is also applicable to a wide range of products where flexibility is required. Further, as described above, the molded product can be stably processed and produced for a long time in a wide range of processing temperatures of 130 to 150 ° C. without requiring special equipment, materials and methods. , Can be easily manufactured. For example, since a molded object is excellent in molding processability, it can be easily manufactured by publicly known general-purpose processing methods, such as a calendar molding method, an injection molding method, an extrusion molding method, a blow molding method, and a press molding method. Moreover, a molded object can be manufactured at low cost, when manufacturing using the above-mentioned resin waste material. As a molded object, it can be used, for example, as a sheet or film used for building materials, civil engineering materials, agricultural materials, packaging materials and the like, fiber materials and the like. Among them, as described above, since the molded body is excellent in thermal stability, weather resistance, cold resistance, flame retardancy, chemical resistance, etc., it is suitable for outdoor applications such as construction materials, civil engineering materials, agricultural materials, and packaging materials. It can be used for As mentioned above, since the molded object concerning this embodiment has the above-mentioned outstanding characteristic, it can be used for a wide range of uses, and industrial use value is high. In addition, a molded object may be formed using the resin blend containing the resin composition of said this embodiment.
次に、本実施形態に係る樹脂組成物、樹脂ブレンド物の製造方法、及び成形体の製造方法を説明する。ただし、これらの製造方法は、一例であり、以下に説明する製造方法に限定されるものではない。 Next, the resin composition, the method for producing a resin blend, and the method for producing a molded product according to the present embodiment will be described. However, these manufacturing methods are merely examples, and the present invention is not limited to the manufacturing methods described below.
実施形態に係る樹脂組成物及び樹脂ブレンド物の製造は、まず、樹脂組成物の原料として、上記した塩化ビニリデン系樹脂、軟質アクリル系樹脂、可塑剤を準備する。なお、塩化ビニリデン樹脂は、樹脂廃材を用いてもよい。また、上記以外の樹脂、上記した熱安定剤、添加剤などの他の成分を含有させる場合は、他の成分を準備する。 In the production of the resin composition and the resin blend according to the embodiment, first, the above-described vinylidene chloride resin, soft acrylic resin, and plasticizer are prepared as raw materials of the resin composition. In addition, you may use resin waste material for vinylidene chloride resin. Moreover, when making it contain other components, such as resin of that excepting the above, the above-mentioned heat stabilizer, and an additive, other components are prepared.
次に、準備した各原料を上記した所定の割合で混合し、混合物を得る。各原料の所定の割合は、塩化ビニリデン樹脂４０〜９７重量部、及び軟質アクリル系樹脂６０〜３重量部の合計１００重量部に対して、可塑剤１〜２７重量部である。また、熱安定剤を含有させる場合、熱安定剤の含有量は、塩化ビニリデン樹脂及び軟質アクリル系樹脂の合計１００重量部０．３〜１０質量部である。また、上記以外の樹脂や添加剤などの他の成分を含有させる場合は、成分に合わせた所定の割合で適宜混合する。 Next, the prepared raw materials are mixed at the predetermined ratio described above to obtain a mixture. The predetermined ratio of each raw material is 1 to 27 parts by weight of a plasticizer with respect to a total of 100 parts by weight of 40 to 97 parts by weight of a vinylidene chloride resin and 60 to 3 parts by weight of a soft acrylic resin. When the heat stabilizer is contained, the content of the heat stabilizer is 100 parts by weight in total of 0.3 to 10 parts by weight in total of vinylidene chloride resin and soft acrylic resin. Moreover, when making it contain other components, such as resin other than the above and an additive, it mixes suitably in the predetermined ratio according to the component.
原料の混合は、任意の方法により行うことができる。例えば、混合は、例えば、商品名「ヘンシェルミキサー」（日本コークス工業株式会社製）、商品名「スーパーミキサー」（カワタ株式会社製）、リボンブレンダー等、公知の混合装置を用いて行うことができる。 The mixing of the raw materials can be performed by any method. For example, the mixing can be performed using a known mixing device such as, for example, trade name "Henshell Mixer" (manufactured by Nippon Coke Industry Co., Ltd.), trade name "Super Mixer" (manufactured by Kawata Co., Ltd.), or ribbon blender. .
なお、原料の混合の際、あるいは原料を混合した後に、原料を混合した混合物の造粒を行ってもよい。造粒は、公知の方法により行うことができる。例えば、造粒は、押出機等を用いた強制造粒法により行うことができる。また、混合及び造粒は、混合装置及び造粒装置を備える装置を用いて、同時に行ってもよい。例えば、混合及び造粒は、ヘンシェルミキサー、スーパーミキサー等を用いて行うことができる。なお、造粒を行うか否かは任意である。例えば、樹脂組成物は、原料を混合した混合物を造粒せずに、溶融混練して冷却することにより製造してもよい。 At the time of mixing the raw materials or after mixing the raw materials, granulation of the mixture obtained by mixing the raw materials may be performed. Granulation can be performed by a known method. For example, granulation can be performed by forced granulation using an extruder or the like. Also, mixing and granulation may be performed simultaneously using an apparatus equipped with a mixing apparatus and a granulation apparatus. For example, mixing and granulation can be performed using a Henschel mixer, a super mixer, and the like. In addition, it is arbitrary whether granulation is performed. For example, the resin composition may be produced by melt-kneading and cooling the mixture in which the raw materials are mixed without granulating the mixture.
次に、原料を混合した混合物を溶融混練し、冷却する。これにより樹脂組成物が完成する。溶融混練は、例えば、公知の溶融混錬装置を用いて行うことができる。なお、溶融混錬の温度及び時間は、樹脂組成物が熱分解しない温度及び時間であれば、任意である。溶融混錬の温度及び時間は、例えば、温度は１３０℃〜１５０℃に設定され、時間は２０分〜６０分程度に設定される。冷却は、原料の混合物を溶融混錬した溶融混錬物を冷却し固化させる。冷却は、任意の方法により行うことができる。例えば、冷却は、溶融混錬物を室温で冷却してもよいし、冷却装置により冷却してもよい。 Next, the mixture obtained by mixing the raw materials is melt-kneaded and cooled. Thereby, the resin composition is completed. Melt-kneading can be performed using a well-known melt-kneading apparatus, for example. In addition, the temperature and time of melt-kneading are arbitrary if it is the temperature and time which a resin composition does not thermally decompose. The temperature and time of the melt-kneading are set, for example, to 130 ° C. to 150 ° C., and the time is set to about 20 minutes to 60 minutes. Cooling cools and solidifies the melt-kneaded product obtained by melt-kneading the mixture of raw materials. The cooling can be performed by any method. For example, the cooling may be cooling the molten mixture at room temperature or may be performed by a cooling device.
また、成形体を製造する場合、上記した原料の混合物又は樹脂組成物を、溶融混錬した後、成形して、冷却する。成形は、例えば、カレンダー成形機、射出成形機、押出し成形機、ブロー成形機、プレス成形機等の成形機を用いて、任意の形状に行うことができる。なお、成形の温度及び時間は、樹脂組成物が熱分解しない温度及び時間であれば任意である。成形の温度及び時間は、例えば、温度は１３０℃〜１５０℃に設定され、時間は２０分〜６０分程度に設定される。 Moreover, when manufacturing a molded object, after melt-kneading the mixture or resin composition of the above-mentioned raw material, it shape | molds and cools. Molding can be performed in any shape using a molding machine such as, for example, a calender molding machine, an injection molding machine, an extrusion molding machine, a blow molding machine, or a press molding machine. In addition, the temperature and time of shaping | molding are arbitrary if it is the temperature and time which a resin composition does not thermally decompose. For example, the temperature is set to 130 ° C. to 150 ° C., and the time is set to about 20 minutes to 60 minutes.
以上のように、本実施形態に係る樹脂組成物の製造方法は、樹脂組成物及び樹脂ブレンド物を容易に製造することができる。また、成形体の製造方法は、成形体を容易に製造することができる。 As mentioned above, the manufacturing method of the resin composition concerning this embodiment can manufacture a resin composition and a resin blend easily. Moreover, the manufacturing method of a molded object can manufacture a molded object easily.
以上のように、本実施形態に係る樹脂組成物の製造方法、樹脂ブレンド物の製造方法は、樹脂組成物及び樹脂ブレンド物を容易に製造することができる。また、本実施形態に係る成形体の製造方法は、成形体を容易に製造することができる。 As mentioned above, the manufacturing method of the resin composition concerning this embodiment, and the manufacturing method of a resin blend can manufacture a resin composition and a resin blend easily. Moreover, the manufacturing method of the molded object which concerns on this embodiment can manufacture a molded object easily.
以下、実施例及び比較例により本発明を具体的に説明するが、本発明はこれらにより何ら制限されるものではない。 Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto.
［実施例１〜１０、比較例１〜４］
（樹脂組成物（成形体）の製造）
原料として、所定量の塩化ビニリデン樹脂、所定量の熱安定剤（ハイドロタルサイト（Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ））、所定量の軟質アクリル系樹脂（クラレ社製、商品名：パラペット、ＳＡ−ＣＷ００１、登録商標）、所定量のエポキシ化エステル系可塑剤（エポキシ化大豆油、アデカ社製、商品名：Ｏ−１３０Ｐ）、所定量のフタル酸系エステル可塑剤（ジ−２−エチルヘキシルフタレート（ＤＯＰ））、所定量の脂肪酸エステル系可塑剤（ジ−２−エチルヘキシルアジペート（ＤＯＡ））を、表１に示す割合で準備し、表１に示すロール温度１３０〜１５５℃の範囲の温度にセットした６インチロールに投入した。そして、５分間混錬し、約０．５ｍｍ厚のシート（樹脂組成物、成形体）を製造した。
[Examples 1 to 10, Comparative Examples 1 to 4]
(Production of Resin Composition (Molded Body))
As a raw material, a predetermined amount of vinylidene chloride resin, a predetermined amount of heat stabilizer (hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3 · 4H 2 O)), a predetermined amount of soft acrylic resin (manufactured by Kuraray Co., Ltd.) Product name: Parapet, SA-CW 001 (registered trademark), predetermined amount of epoxidized ester plasticizer (epoxidized soybean oil, manufactured by Adeka, trade name: O-130P), predetermined amount of phthalic acid ester plasticizer ( Di-2-ethylhexyl phthalate (DOP), a predetermined amount of fatty acid ester plasticizer (di-2-ethylhexyl adipate (DOA)) were prepared in the proportions shown in Table 1, and the roll temperatures shown in Table 1 were 130 to 155. It was loaded on a 6 inch roll set to a temperature in the range of ° C. And it knead | mixed for 5 minutes, and manufactured the sheet (resin composition, molded object) of about 0.5 mm thickness.
なお、用いた原料のうち、塩化ビニリデン樹脂は、塩化ビニリデン由来の構成単位を６０重量％以上と、塩化ビニル由来の構成単位を１０〜２０％とを含有する塩化ビニリデン−塩化ビニル共重合体であるラップの廃材（樹脂廃材）を用いた。なお、ラップの廃材は、フィルム延伸後の廃材を一辺の長さを５〜５０ｍｍ程度に粉砕したもの、または平均粒径が３〜６ｍｍのフィルム延伸前の廃材を用いた。また、用いた軟質アクリル系樹脂（クラレ社製、商品名：パラペット、ＳＡ−ＣＷ００１）は、メタクリル酸メチルとアクリル酸メチルとの共重合体をベースに、（メタ）アクリル酸ブチル、更に（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２エチルヘキシル等の（メタ）アクリル酸系エステル、あるいはスチレンなどを付与した共重合体である。各原料の配合割合を、表１に示す。 Among the raw materials used, a vinylidene chloride resin is a vinylidene chloride-vinyl chloride copolymer containing 60% by weight or more of a vinylidene chloride-derived constitutional unit and 10 to 20% of a vinyl chloride-derived constitutional unit. A certain wrap waste (resin waste) was used. In addition, as a waste material of a wrap, the waste material after extending | stretching the film in which the length of one side was grind | pulverized to about 5-50 mm, or the waste material before film extending | stretching whose average particle diameter is 3-6 mm was used. In addition, the used soft acrylic resin (manufactured by Kuraray, trade name: Parapet, SA-CW 001) is a copolymer of methyl methacrylate and methyl acrylate as a base, butyl (meth) acrylate, (meth) ) A copolymer obtained by adding a (meth) acrylic acid ester such as hexyl acrylate or 2-ethylhexyl (meth) acrylate, or styrene. The blend ratio of each raw material is shown in Table 1.
（各種評価）
樹脂組成物の成膜性を評価した。成膜性は、製造した樹脂組成物（成形体）のシートを目視により評価した。成膜性は、表面が滑らかな状態で、フローマーク、浪打、ざらつきのすべてがなく、ロールに良好に巻き付き、良好にシート状に形成されたものを◎；表面が滑らかな状態で、フローマーク、浪打、ざらつきのすべてがなく、ロールへの良好に巻き付きが若干悪いが良好にシート状に形成されたものを〇；フローマーク、浪打、ざらつきのいずれかが見られたもの、良好にシート状に形成されなかったものを×と判定し、「◎」及び「〇」を合格とした。結果を表１に示す。また、比重を、ＪＩＳＫ７１１２に準じて、水中法（水中置換法）により測定した。また、硬度を、ＪＩＳ Ｋ ７２０６に準じて測定した。難燃性は、ＵＬ９４燃焼試験に準拠して評価した。耐候性（耐光性）は、岩崎電気株式会社製、型式：ＸＥＲ−Ｗ７５の促進耐候性試験装置（フェードメーター）を用いて、キセノンアークランプで光を２５０時間、５００時間照射した後、樹脂の変色具合を観察し、２５０時間照射後に変色が見られたものを「×」、２５０時間照射後に変色がなかったものを「〇」、５００時間照射後に変色がなかったものを「◎」と判定し、「◎」及び「○」を合格とした。耐寒性は、樹脂を−５℃で保持した冷蔵庫に６０分以上放置した後、冷蔵庫から取り出して１８０℃に折り曲げたときに割れるか否かで評価し、割れなかったものを「○」とし合格とし、割れたものを「×」とし不合格とした。
(Various evaluations)
The film formability of the resin composition was evaluated. The film formability evaluated the sheet | seat of the manufactured resin composition (molded object) by visual observation. The film forming property is that the surface is smooth, there is no flow mark, no impact, no roughness, everything is wound on the roll well, and the sheet is well formed ◎; the surface is smooth, the flow mark There is no all strikes and roughness, and the winding on the roll is a little bad, but it is well formed into a sheet-like ○; flow mark, sanding and scratched, and good sheet-like Those which were not formed were judged to be x, and "o" and "o" were taken as passing. The results are shown in Table 1. Moreover, specific gravity was measured by the underwater method (underwater substitution method) according to JISK7112. The hardness was also measured according to JIS K 7206. The flame retardancy was evaluated in accordance with the UL 94 combustion test. The weather resistance (light resistance) was determined by irradiating light with a xenon arc lamp for 250 hours and 500 hours using an accelerated weathering test apparatus (fade meter) manufactured by Iwasaki Electric Co., Ltd., model: XER-W75, The degree of color change was observed, and those with a color change after irradiation for 250 hours were evaluated as "x", those without color change after 250 hours of irradiation were evaluated as "o", those with no color change after irradiation for 500 hours were evaluated as "o". And "o" and "o" were passed. Cold resistance is evaluated by leaving the resin in a refrigerator held at -5 ° C for 60 minutes or more, and then taking it out of the refrigerator and bending it at 180 ° C to evaluate whether it breaks or not. And, the cracked thing was made into "x" and it was disqualified.
以下、実施例及び比較例の結果について説明する。実施例１〜実施例１０および比較例１〜４に示したように、実施例１〜実施例１０に示す本発明の塩化ビニリデン樹脂組成物（成形体）は、容易に製造することができ、塩化ビニリデン樹脂が有する物理的特性である耐熱性、難燃性、耐薬品性等の性質、及び軟質アクリル樹脂の物理的特性である耐候性、耐寒性を保持するとともに、柔軟化の範囲及び汎用加工設備での加工条件の範囲を拡大することができることが確認される。 Hereinafter, the results of Examples and Comparative Examples will be described. As shown in Examples 1 to 10 and Comparative Examples 1 to 4, the vinylidene chloride resin composition (molded product) of the present invention shown in Examples 1 to 10 can be easily manufactured, The physical properties of vinylidene chloride resin, such as heat resistance, flame retardancy, chemical resistance, etc., and the physical properties of soft acrylic resin, such as weather resistance and cold resistance, while maintaining the range and flexibility of softening It is confirmed that the range of processing conditions in processing equipment can be expanded.
なお、実施例２から実施例４において、可塑剤の種類を検討した。実施例２から実施例４において、それぞれ、塩化ビニリデン樹脂及び軟質アクリル樹脂の合計１００重量部に対して、塩化ビニル樹脂に用いられる異なる可塑剤（フタル酸系エステル可塑剤（ＤＯＰ）、脂肪酸エステル系可塑剤（ＤＯＡ）、エポキシ化系可塑剤（エポキシ化大豆油））５．０重量部添加した。この結果から、異なる可塑剤においても、上記した本実施形態の塩化ビニリデン樹脂組成物（成形体）が製造できることが確認される。 In Examples 2 to 4, the type of plasticizer was examined. In Example 2 to Example 4, different plasticizers used for vinyl chloride resin (phthalic acid ester plasticizer (DOP), fatty acid ester type with respect to 100 parts by weight in total of vinylidene chloride resin and soft acrylic resin respectively) 5.0 parts by weight of a plasticizer (DOA) and an epoxidized plasticizer (epoxidized soybean oil) were added. From this result, it is confirmed that the vinylidene chloride resin composition (molded product) of the present embodiment described above can be produced even with different plasticizers.
また、実施例２、実施例５から実施例１０において、軟質アクリル系樹脂及び可塑剤の含有量を検討した。実施例２、実施例５から実施例１０において、軟質アクリル系樹脂の含有量を５〜５０重量部、また、可塑剤の含有量を５〜２５重量部に変化させて、樹脂組成物の特性を検討した。この結果から、異なる軟質アクリル系樹脂及び可塑剤の含有量においても、上記した本実施形態の塩化ビニリデン樹脂組成物（成形体）が製造できることが確認される。また、塩化ビニリデン樹脂に対する軟質アクリル系樹脂の割合を多くすることにより、軟質アクリル系樹脂の特性（柔軟性、耐候性等）をより多く付与でき、柔軟化の範囲を拡大することができることが確認される。なお、塩化ビニリデン樹脂に対する軟質アクリル系樹脂の割合を多くすると、樹脂組成物の難燃性は優れたものであるが若干低下する。また、塩化ビニリデン樹脂に対する、可塑剤及び軟質アクリル系樹脂の含有量（合計量）を多くすることにより、加工温度を低くすることができ、言い換えれば耐熱性を向上させることができ、加工条件の範囲を拡大できることが確認される。 Moreover, in Example 2, Example 5 to Example 10, content of soft acrylic resin and a plasticizer was examined. In Example 2, Example 5 to Example 10, the content of the soft acrylic resin is changed to 5 to 50 parts by weight, and the content of the plasticizer is changed to 5 to 25 parts by weight to obtain the characteristics of the resin composition It was investigated. From this result, it is confirmed that the vinylidene chloride resin composition (molded product) of the present embodiment described above can be produced even with different contents of the soft acrylic resin and the plasticizer. In addition, it is confirmed that by increasing the ratio of the soft acrylic resin to the vinylidene chloride resin, more characteristics (softness, weather resistance, etc.) of the soft acrylic resin can be imparted, and the range of softening can be expanded. Be done. In addition, when the ratio of the soft acrylic resin to the vinylidene chloride resin is increased, the flame retardancy of the resin composition is excellent, but it slightly decreases. Further, by increasing the content (total amount) of the plasticizer and the soft acrylic resin relative to the vinylidene chloride resin, the processing temperature can be lowered, in other words, the heat resistance can be improved, and the processing conditions It is confirmed that the range can be expanded.
また、比較例１において、軟質アクリル系樹脂及び可塑剤を含有させないときの樹脂組成物について検討した。比較例１においては、ロールにはかろうじて巻き付いたが、樹脂のゲル化が進行せずシートが形成されなかった。なお、この組成の場合、低温では加工が不良のため、ロール加工温度を１５５℃に設定した。このことから、軟質アクリル系樹脂及び可塑剤は、樹脂組成物の耐熱性の向上、及び成膜性（加工性）の向上に寄与することが推察される。 Moreover, in the comparative example 1, it examined about the resin composition at the time of not containing soft acrylic resin and a plasticizer. In Comparative Example 1, the roll was barely wound, but the gelation of the resin did not proceed and no sheet was formed. In the case of this composition, the rolling processing temperature was set at 155 ° C., because the processing was poor at low temperatures. From this, it is speculated that the soft acrylic resin and the plasticizer contribute to the improvement of the heat resistance of the resin composition and the improvement of the film forming property (processability).
また、比較例２において、軟質アクリル系樹脂を含有させないときの樹脂組成物について検討した。比較例２においては、比較例１と同様に、ロールにはかろうじて巻き付いたが、シートが形成されなかった。なお、この組成の場合、低温では加工が不良のため、ロール加工温度を１５０℃に設定した。このことから、可塑剤は、樹脂組成物の耐熱性の向上、及び成膜性（加工性）の向上に寄与することが推察される。 Moreover, in the comparative example 2, it examined about the resin composition at the time of not containing soft acrylic resin. In Comparative Example 2, as in Comparative Example 1, the roll was barely wound, but no sheet was formed. In addition, in the case of this composition, since processing was inferior at low temperature, the roll processing temperature was set to 150 degreeC. From this, it is presumed that the plasticizer contributes to the improvement of the heat resistance of the resin composition and the improvement of the film forming property (processability).
また、比較例３において、軟質アクリル系樹脂を少量含有させ、可塑剤を含有させないときの樹脂組成物について検討した。比較例３においては、比較例１と同様に、ロールにはかろうじて巻き付いたが、シートが形成されなかった。なお、この組成の場合、低温では加工が不良のため、ロール加工温度を１５０℃に設定した。このことから、所定量の軟質アクリル系樹脂及び可塑剤が、樹脂組成物の耐熱性の向上、及び成膜性（加工性）の向上に寄与することが推察される。 Moreover, in the comparative example 3, a small amount of soft acrylic resin was contained, and the resin composition when not containing a plasticizer was examined. In Comparative Example 3, as in Comparative Example 1, the roll was barely wound, but no sheet was formed. In addition, in the case of this composition, since processing was inferior at low temperature, the roll processing temperature was set to 150 degreeC. From this, it is inferred that predetermined amounts of the soft acrylic resin and the plasticizer contribute to the improvement of the heat resistance of the resin composition and the improvement of the film forming property (processability).
また、比較例４において、可塑剤の量を多くしたときの樹脂組成物について検討した。比較例４においては、比較例１と同様に、ロールにはかろうじて巻き付いたが、粘着してシートが形成されなかった。このことから、可塑剤の量が多い場合、加工性が悪化することが確認される。そして、所定量の軟質アクリル系樹脂及び可塑剤が、樹脂組成物の耐熱性の向上、及び成膜性（加工性）の向上に寄与することが推察される。 Moreover, in the comparative example 4, it examined about the resin composition when the quantity of a plasticizer was increased. In Comparative Example 4, as in Comparative Example 1, the roll was barely wound around, but no sheet was formed by sticking. From this, it is confirmed that when the amount of plasticizer is large, the processability is deteriorated. Then, it is speculated that predetermined amounts of the soft acrylic resin and the plasticizer contribute to the improvement of the heat resistance of the resin composition and the improvement of the film forming property (processability).
以上のように、本実施形態の樹脂組成物は、塩化ビニリデン樹脂が有する物理的特性である耐熱性、難燃性、耐薬品性等の性質、及び軟質アクリル樹脂の物理的特性である耐候性、耐寒性を保持するとともに、柔軟化の範囲及び汎用加工設備での加工条件の範囲を拡大することができる。 As described above, the resin composition of the present embodiment has the physical properties of vinylidene chloride resin, such as heat resistance, flame retardancy, chemical resistance, etc., and the physical properties of soft acrylic resin, such as weather resistance. While maintaining cold resistance, it is possible to expand the range of flexibility and the range of processing conditions in general-purpose processing equipment.
以上、本発明の実施形態及び実施例について説明したが、本発明の技術範囲は、上記の実施形態や実施例に限定されるものではない。例えば、上記の実施形態や実施例で説明した要件の１つ以上は、省略されることがある。また、上記の実施形態や実施例で説明した要件は、適宜組み合わせることができる。
Although the embodiments and examples of the present invention have been described above, the technical scope of the present invention is not limited to the above embodiments and examples. For example, one or more of the requirements described in the above embodiments and examples may be omitted. Further, the requirements described in the above embodiments and examples can be combined as appropriate.
Claims (6)
帯電防止可塑剤は、アジピン酸系エステル、フタル酸系エステル、及び第４級アンモニウム塩のうち少なくとも１種を含有する。 The plasticizer includes phthalic acid ester plasticizer, fatty acid ester plasticizer, phosphoric acid ester plasticizer, epoxy plasticizer, trimellitic acid ester plasticizer, polyester plasticizer, antistatic having the following characteristics The vinylidene chloride resin composition of Claim 1 or Claim 2 which is at least 1 sort (s) selected from the group which consists of a plasticizer and a benzoate ester plasticizer.
The antistatic plasticizer contains at least one of an adipic acid ester, a phthalic acid ester, and a quaternary ammonium salt.
前記塩化ビニリデン樹脂組成物を１５重量％以上含む、樹脂ブレンド物。
A vinyl chloride resin composition according to any one of claims 1 to 5, and a resin blend comprising a resin other than the vinylidene chloride resin composition,
A resin blend comprising 15% by weight or more of the vinylidene chloride resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017074327A JP2018177849A (en) | 2017-04-04 | 2017-04-04 | Vinylidene chloride resin composition, and resin blend |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017074327A JP2018177849A (en) | 2017-04-04 | 2017-04-04 | Vinylidene chloride resin composition, and resin blend |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2018177849A true JP2018177849A (en) | 2018-11-15 |
Family
ID=64281265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017074327A Pending JP2018177849A (en) | 2017-04-04 | 2017-04-04 | Vinylidene chloride resin composition, and resin blend |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2018177849A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5333250A (en) * | 1976-09-08 | 1978-03-29 | Kureha Chem Ind Co Ltd | Vinylidene chloride resin film |
| JPH08208926A (en) * | 1994-11-18 | 1996-08-13 | Wr Grace & Co Connecticut | Vinylidene chloride composition and film with controlled gaspermeability |
| JPH10101878A (en) * | 1996-10-03 | 1998-04-21 | Kureha Chem Ind Co Ltd | Vinylidene chloride-based resin composition and molded product thereof |
| JP2008013735A (en) * | 2006-07-04 | 2008-01-24 | Daido Kasei Kk | Vinylidene chloride resin composition |
| JP2009138314A (en) * | 2007-12-10 | 2009-06-25 | Kaneka Corp | Artificial hair fiber, artificial hair, and hair accessory product composed of the artificial hair |
| JP2011122149A (en) * | 2009-11-20 | 2011-06-23 | Dow Global Technologies Llc | Printable monolayer polyvinylidene chloride structure |
| JP2015502984A (en) * | 2011-10-14 | 2015-01-29 | クライオバック・インコーポレイテツド | Polymer film containing odor absorbing PVDC blend |
| JP2016204538A (en) * | 2015-04-23 | 2016-12-08 | 大同化成株式会社 | Vinylidene chloride resin composition |
-
2017
- 2017-04-04 JP JP2017074327A patent/JP2018177849A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5333250A (en) * | 1976-09-08 | 1978-03-29 | Kureha Chem Ind Co Ltd | Vinylidene chloride resin film |
| JPH08208926A (en) * | 1994-11-18 | 1996-08-13 | Wr Grace & Co Connecticut | Vinylidene chloride composition and film with controlled gaspermeability |
| JPH10101878A (en) * | 1996-10-03 | 1998-04-21 | Kureha Chem Ind Co Ltd | Vinylidene chloride-based resin composition and molded product thereof |
| JP2008013735A (en) * | 2006-07-04 | 2008-01-24 | Daido Kasei Kk | Vinylidene chloride resin composition |
| JP2009138314A (en) * | 2007-12-10 | 2009-06-25 | Kaneka Corp | Artificial hair fiber, artificial hair, and hair accessory product composed of the artificial hair |
| JP2011122149A (en) * | 2009-11-20 | 2011-06-23 | Dow Global Technologies Llc | Printable monolayer polyvinylidene chloride structure |
| JP2015502984A (en) * | 2011-10-14 | 2015-01-29 | クライオバック・インコーポレイテツド | Polymer film containing odor absorbing PVDC blend |
| JP2016204538A (en) * | 2015-04-23 | 2016-12-08 | 大同化成株式会社 | Vinylidene chloride resin composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2014091867A1 (en) | Vinyl chloride resin composition for powder molding, vinyl chloride resin molded article and laminate | |
| WO2009107463A1 (en) | Vinyl chloride resin composition for powder molding, vinyl chloride resin molded body, laminate, automobile interior material, and method for producing vinyl chloride resin composition for powder molding | |
| JP5518507B2 (en) | Method for producing master batch pellet and propylene resin composition molded body | |
| CN106317586A (en) | Injection molded antistatic high-rigidity LLDPE (Linear Low Density Polyethylene) resin and preparation method thereof | |
| JP6039712B2 (en) | Eco-friendly soft MBS resin composition, method for producing the same, and vinyl leather using the composition | |
| CN106604963A (en) | Stabilizer composition for vinyl chloride resin, vinyl chloride resin composition using said stabilizer composition, and molded article obtained from said resin composition | |
| JP6724787B2 (en) | Vinyl chloride resin composition for powder molding, method for producing the same, vinyl chloride resin molding, method for producing the same, and laminate | |
| JPH08239516A (en) | Cold-resistant halogen-free flame-retardant polyolefin resin composition | |
| JP5848789B2 (en) | Flame-retardant resin composition and molded body using the same | |
| HUE025595T2 (en) | Stabiliser systems for polymers containing halogen | |
| JP6926391B2 (en) | Vinylidene chloride resin composition, resin blend, and molded article | |
| JP2018177849A (en) | Vinylidene chloride resin composition, and resin blend | |
| JP2016204538A (en) | Vinylidene chloride resin composition | |
| JP6819675B2 (en) | Vinyl chloride resin composition, vinyl chloride resin molded product, and laminate | |
| JP2005008771A (en) | Polyester-based resin composition for calendering and film or sheet using the same resin composition | |
| JP2018177848A (en) | Vinylidene chloride resin composition, method for producing vinylidene chloride resin composition, resin blend, vinylidene chloride resin foam, and method for producing vinylidene chloride resin foam | |
| JP6567860B2 (en) | Vinylidene chloride resin composition | |
| JP7192305B2 (en) | Heat storage resin composition and method for producing the same | |
| JPH01308439A (en) | Production of molding | |
| JP6863293B2 (en) | Vinyl chloride resin composition, vinyl chloride resin molded product and laminate | |
| JP2008013735A (en) | Vinylidene chloride resin composition | |
| JP2017141311A (en) | Liquid stabilizer and thermoplastic resin composition containing liquid stabilizer | |
| KR20180115296A (en) | As a carrier system for CFA of foamed polystyrene, a liquid modifier | |
| JP2004175868A (en) | Halogen-containing resin composition | |
| JP2006124502A (en) | Stabilizer for halogen-containing resin, and halogen-containing resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200313 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20210107 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210119 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20210720 |