JP7581764B2 - Processing aid and resin composition - Google Patents
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- 239000006057 Non-nutritive feed additive Substances 0.000 title claims description 68
- 239000011342 resin composition Substances 0.000 title claims description 41
- 229920000642 polymer Polymers 0.000 claims description 143
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 67
- 229920002554 vinyl polymer Polymers 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 48
- -1 vinyl nitrile Chemical class 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 229920001577 copolymer Polymers 0.000 claims description 33
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 26
- 230000009477 glass transition Effects 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 16
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000000843 powder Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 230000000903 blocking effect Effects 0.000 description 15
- 239000000155 melt Substances 0.000 description 15
- 238000000465 moulding Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 210000000497 foam cell Anatomy 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 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 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 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 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000005143 pyrolysis gas chromatography mass spectroscopy Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、樹脂成型時の加工性を改善する加工助剤、および、それを含む樹脂組成物に関するものである。 The present invention relates to a processing aid that improves processability during resin molding, and a resin composition containing the same.
樹脂の成形加工時の溶融張力は、成形加工操作を成功させる上で鍵となる因子である。例えば、溶融張力が高いと、発泡成形においては、発泡セルの構造が固定され、均質で発泡倍率の高い成形品が得られる。異形押出では、溶融した樹脂をダイ又はサイジングを通して引き取ることが容易になり、生産性の向上に繋がる。このように、樹脂の溶融張力を高めることで、成形加工において多くの利点が得られる。 The melt tension of the resin during molding is a key factor in making the molding process successful. For example, high melt tension fixes the foam cell structure in foam molding, resulting in homogeneous molded products with a high expansion ratio. In profile extrusion, it becomes easier to pull the molten resin through a die or sizing, leading to improved productivity. In this way, increasing the melt tension of the resin provides many advantages in molding processes.
樹脂組成物の溶融張力を高める方法として、分子量の高いマトリックス樹脂を使用する方法が知られている。しかし、マトリックス樹脂の分子量を高くすると、溶融張力に伴って溶融粘度も上昇し、一般的な成形装置では加工が困難になる場合がある。加えて、塩化ビニル系樹脂などの溶融に時間が掛かる樹脂は、分子量を高くすると更に溶融が遅くなり、加工性が著しく損なわれる。 One method known for increasing the melt tension of a resin composition is to use a matrix resin with a high molecular weight. However, when the molecular weight of the matrix resin is increased, the melt viscosity also increases along with the melt tension, which can make processing difficult using standard molding equipment. In addition, for resins that take a long time to melt, such as vinyl chloride resins, increasing the molecular weight will make the melting process even slower, significantly impairing processability.
上述の課題を解決するために、樹脂組成物に高分子量の加工助剤を添加する方法が広く知られている（特許文献１及び２）。 To solve the above problems, a method of adding a high molecular weight processing aid to a resin composition is widely known (Patent Documents 1 and 2).
特許文献１では、加工助剤のガラス転移温度を低くすることで、樹脂への分散性に優れ、加工時の溶融張力を向上させる方法が開示されている。しかしながら、ガラス転移温度が低い加工助剤は粉体粒子が融着し易いため、加工助剤の粉体流動性が低位であり、樹脂の成型加工工程において、加工助剤の滞留やブロッキングが発生し、樹脂成形品の生産性を低下させる要因となる。 Patent Document 1 discloses a method of lowering the glass transition temperature of a processing aid to improve dispersibility in resin and melt tension during processing. However, processing aids with low glass transition temperatures have low powder flowability because the powder particles are prone to fusing, which can cause retention and blocking of the processing aid during the resin molding process, resulting in reduced productivity of resin molded products.
特許文献２では、ガラス転移温度が低い重合体を、ガラス転移温度が高い重合体で覆うことで、粉体の融着を防止し、加工助剤の粉体流動性を改善できることが開示されている。しかしながら、ガラス転移温度が高い重合体は樹脂への分散性が低位であるため、溶融樹脂の張力に偏りが生じて均質な加工に悪影響を与え、加工助剤として十分な性能を得られていない。 Patent Document 2 discloses that by covering a polymer with a low glass transition temperature with a polymer with a high glass transition temperature, it is possible to prevent powder fusion and improve the powder flowability of the processing aid. However, polymers with high glass transition temperatures have low dispersibility in resins, which causes uneven tension in the molten resin and adversely affects uniform processing, making it difficult to obtain sufficient performance as a processing aid.
本発明は上記課題を解決するものであり、樹脂組成物の溶融張力を均質に向上させて、成形加工性を改善したり、加工助剤の粉体流動性を改善して、優れた耐ブロッキング性を実現したりできる加工助剤を提供することを目的とする。 The present invention aims to solve the above problems by providing a processing aid that can uniformly improve the melt tension of a resin composition to improve molding processability, and improve the powder fluidity of the processing aid to achieve excellent blocking resistance.
本発明は下記の態様を有する。
［１］重量平均分子量が２００万以上で、ガラス転移温度が５０℃以下である重合体Ａと、重量平均分子量が１５０万以下で、ガラス転移温度が７０℃以上である重合体Ｂと、を含む加工助剤であって、前記重合体Ｂよりも前記重合体Ａが多く含まれる加工助剤。
［２］前記重合体Ａの構成単位として、炭素数が２以上のアルキル基を有するアルキル（メタ）アクリレートの単位を１種以上含む、［１］に記載の加工助剤。
［３］前記重合体Ｂの構成単位として、メチル（メタ）アクリレート、芳香族ビニルとビニルニトリルの共重合体、及びビニルハロゲン化物からなる群から選択される１種以上の単位を含む、［１］または［２］に記載の加工助剤。
［４］前記重合体Ａと前記重合体Ｂの総質量１００質量％に対する、重合体Ａの割合が５５質量％以上９９質量％以下であり、前記重合体Ｂの割合が１質量％以上４５質量％以下である、［１］～［３］のいずれかに記載の加工助剤。
［５］前記重合体Ａを構成する全構成単位に対する炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位の割合が２０質量％以上１００質量％以下であり、メチル（メタ）アクリレート、芳香族ビニルとビニルニトリルの共重合体、及びビニルハロゲン化物の単位の合計割合が０質量％以上８０質量％以下である、［１］～［４］のいずれかに記載の加工助剤。
［６］前記重合体Ｂを構成する全構成単位に対する炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位の割合が０質量％以上４５質量％以下であり、メチル（メタ）アクリレート、芳香族ビニルとビニルニトリルの共重合体、及びビニルハロゲン化物の単位の合計割合が５５質量％以上１００質量％以下である、［１］～［５］のいずれかに記載の加工助剤。
［７］前記重合体Ａの全構成単位に対するメチルメタクリレートの単位の割合が１質量％以上８０質量％以下である、［１］～［６］のいずれかに記載の加工助剤。
［８］前記重合体Ｂの全構成単位に対するメチルメタクリレートの単位の割合が６５質量％以上１００質量％以下である、［１］～［７］のいずれかに記載の加工助剤。
［９］重量平均分子量が２００万以上で、ガラス転移温度が５０℃以下である重合体Ａと、重量平均分子量が１５０万以下で、ガラス転移温度が７０℃以上である重合体Ｂと、マトリックス樹脂と、を含み、前記重合体Ｂよりも前記重合体Ａが多く含まれる、樹脂組成物。
［１０］前記マトリックス樹脂１００質量部に対する前記重合体Ａと前記重合体Ｂの合計割合が０．１質量部以上３０質量部以下である、［９］に記載の樹脂組成物。
［１１］前記マトリックス樹脂が塩化ビニル系樹脂である、［９］又は［１０］に記載の樹脂組成物。
The present invention has the following aspects.
[1] A processing aid comprising: a polymer A having a weight-average molecular weight of 2,000,000 or more and a glass transition temperature of 50° C. or less; and a polymer B having a weight-average molecular weight of 1,500,000 or less and a glass transition temperature of 70° C. or more, wherein the processing aid contains more of the polymer A than the polymer B.
[2] The processing aid according to [1], wherein the polymer A contains, as a structural unit thereof, one or more units of alkyl (meth)acrylate having an alkyl group having two or more carbon atoms.
[3] The processing aid according to [1] or [2], which contains one or more units selected from the group consisting of methyl (meth)acrylate, a copolymer of aromatic vinyl and vinyl nitrile, and a vinyl halide as a constituent unit of the polymer B.
[4] The proportion of polymer A is 55% by mass or more and 99% by mass or less, and the proportion of polymer B is 1% by mass or more and 45% by mass or less, relative to 100% by mass of the total mass of polymer A and polymer B. [1] Any of the processing aids described in [1] to [3].
[5] The processing aid according to any one of [1] to [4], wherein the ratio of one or more alkyl (meth)acrylate units having an alkyl group having two or more carbon atoms to all structural units constituting the polymer A is 20% by mass or more and 100% by mass or less, and the total ratio of methyl (meth)acrylate, a copolymer of aromatic vinyl and vinyl nitrile, and a vinyl halide unit is 0% by mass or more and 80% by mass or less.
[6] The processing aid according to any one of [1] to [5], wherein the ratio of one or more alkyl (meth)acrylate units having an alkyl group having two or more carbon atoms to all structural units constituting the polymer B is 0% by mass or more and 45% by mass or less, and the total ratio of methyl (meth)acrylate, a copolymer of aromatic vinyl and vinyl nitrile, and a vinyl halide unit is 55% by mass or more and 100% by mass or less.
[7] The processing aid according to any one of [1] to [6], wherein the ratio of methyl methacrylate units to all structural units of the polymer A is 1% by mass or more and 80% by mass or less.
[8] The processing aid according to any one of [1] to [7], wherein the ratio of methyl methacrylate units to all structural units of the polymer B is 65% by mass or more and 100% by mass or less.
[9] A resin composition comprising: a polymer A having a weight-average molecular weight of 2,000,000 or more and a glass transition temperature of 50° C. or less; a polymer B having a weight-average molecular weight of 1,500,000 or less and a glass transition temperature of 70° C. or more; and a matrix resin, wherein the polymer A is contained in a larger amount than the polymer B.
[10] The resin composition according to [9], wherein the total ratio of the polymer A and the polymer B to 100 parts by mass of the matrix resin is 0.1 parts by mass or more and 30 parts by mass or less.
[11] The resin composition according to [9] or [10], wherein the matrix resin is a vinyl chloride resin.
本発明によれば、樹脂組成物の溶融張力を均質に向上させて、成形加工性を改善でき、加工助剤の粉体流動性を改善して、優れた耐ブロッキング性を実現できる加工助剤を提供することができる。 The present invention provides a processing aid that can uniformly improve the melt tension of a resin composition, improve molding processability, and improve the powder flowability of the processing aid to achieve excellent blocking resistance.
以下の用語の定義は、本明細書及び特許請求の範囲にわたって適用される。
「（メタ）アクリレート」とは、「アクリレート」または「メタクリレート」を意味する。
The following definitions of terms apply throughout the specification and claims.
"(Meth)acrylate" means "acrylate" or "methacrylate".
以下、本発明を詳細に説明する。
＜加工助剤＞
本発明の加工助剤は、重合体Ａと重合体Ｂを含むもので、これらに加えて第三成分などを含んでもよい。具体的には、少なくとも、加工助剤は、重量平均分子量が２００万以上であり、かつガラス転移温度が５０℃以下である重合体Ａと、重量平均分子量が１５０万以下であり、かつガラス転移温度が７０℃以上である重合体Ｂと、を含み、さらに、前記重合体Ｂよりも前記重合体Ａが多く含まれる。樹脂組成物が、当該加工助剤を含有することにより、メカニズムは明らかではないが、樹脂組成物の溶融張力が均質に向上されるとともに、成形加工性、加工助剤の粉体流動性が改善され、優れた耐ブロッキング性を実現することができる。
The present invention will be described in detail below.
<Processing aids>
The processing aid of the present invention contains polymer A and polymer B, and may further contain a third component. Specifically, the processing aid contains at least polymer A having a weight average molecular weight of 2,000,000 or more and a glass transition temperature of 50° C. or less, and polymer B having a weight average molecular weight of 1,500,000 or less and a glass transition temperature of 70° C. or more, and further contains more polymer A than polymer B. Although the mechanism is not clear, when the resin composition contains the processing aid, the melt tension of the resin composition is uniformly improved, and the molding processability and the powder flowability of the processing aid are improved, thereby achieving excellent blocking resistance.
本発明の加工助剤に含まれる重合体Ａと重合体Ｂの比率は、上述の通り重合体Ｂよりも重合体Ａが多く含まれる、すなわち、重合体Ａと重合体Ｂの総質量１００質量％に対する重合体Ａの割合が５０質量％よりも大きければ特段の制限はないが、良好な加工性と粉体取扱い性を得る観点から、重合体Ａと重合体Ｂの総質量を１００質量％として、重合体Ａが５５質量％以上９９質量％以下であり、重合体Ｂが１質量％以上４５質量％以下であることが好ましく、重合体Ａが７０質量％以上９９質量％以下であり、重合体Ｂが１質量％以上３０質量％以下であることがより好ましく、重合体Ａが７５質量％以上９５質量％以下であり、重合体Ｂが５質量％以上２５質量％以下であることが特に好ましい。 The ratio of polymer A to polymer B contained in the processing aid of the present invention is not particularly limited as long as the polymer A is contained in a larger amount than the polymer B as described above, that is, the ratio of polymer A to the total mass of polymer A and polymer B (100% by mass) is greater than 50% by mass. However, from the viewpoint of obtaining good processability and powder handling, it is preferable that the total mass of polymer A and polymer B is 100% by mass, and that polymer A is 55% by mass to 99% by mass and polymer B is 1% by mass to 45% by mass. It is more preferable that polymer A is 70% by mass to 99% by mass and polymer B is 1% by mass to 30% by mass. It is particularly preferable that polymer A is 75% by mass to 95% by mass and polymer B is 5% by mass to 25% by mass.
本発明の加工助剤の重量平均分子量は、良好な加工性を得る観点から、２００万以上が好ましく、３００万以上がより好ましく、４００万以上が特に好ましい。 From the viewpoint of obtaining good processability, the weight average molecular weight of the processing aid of the present invention is preferably 2 million or more, more preferably 3 million or more, and particularly preferably 4 million or more.
＜重合体Ａ＞
本発明の重合体Ａの重量平均分子量は、ラジカル重合開始剤、重合温度、重合時間を変更することで調整でき、良好な加工性を得る観点から、下限側は２００万以上が好ましく、３００万以上がより好ましく、４００万以上が特に好ましく、４５０万以上が最も好ましく、一方、上限側は１０００万以下が好ましく、８００万以下がより好ましく、６００万以下が特に好ましい。すなわち、重合体Ａの重量平均分子量は、上下限を上述の範囲で選択することが好ましいが、なかでも、４００万以上１０００万以下が好ましく、４５０万以上１０００万以下が特に好ましく、４５０万以上８００万以下が最も好ましい。
<Polymer A>
The weight-average molecular weight of the polymer A of the present invention can be adjusted by changing the radical polymerization initiator, polymerization temperature, and polymerization time, and from the viewpoint of obtaining good processability, the lower limit is preferably 2 million or more, more preferably 3 million or more, particularly preferably 4 million or more, and most preferably 4.5 million or more, while the upper limit is preferably 10 million or less, more preferably 8 million or less, and particularly preferably 6 million or less. That is, it is preferable to select the upper and lower limits of the weight-average molecular weight of the polymer A within the above-mentioned range, and among them, it is preferably 4 million or more and 10 million or less, particularly preferably 4.5 million or more and 10 million or less, and most preferably 4.5 million or more and 8 million or less.
本発明の重合体Ａのガラス転移温度は、モノマーの仕込みを変えることにより調整でき、良好な加工性を得る観点から、５０℃以下が好ましく、０℃以上４５℃以下がより好ましく、１５℃以上４０℃以下が特に好ましい。 The glass transition temperature of the polymer A of the present invention can be adjusted by changing the monomer charge, and from the viewpoint of obtaining good processability, it is preferably 50°C or less, more preferably 0°C or more and 45°C or less, and particularly preferably 15°C or more and 40°C or less.
本発明の重合体Ａの構成単位として、炭素数が２以上のアルキル基を有するアルキル（メタ）アクリレートの単位を含むことが好ましく、炭素数が２以上のアルキル基を有するアルキルアクリレートの単位を含むことがより好ましい。 As a structural unit of the polymer A of the present invention, it is preferable to include an alkyl (meth)acrylate unit having an alkyl group with 2 or more carbon atoms, and it is more preferable to include an alkyl acrylate unit having an alkyl group with 2 or more carbon atoms.
炭素数が２以上のアルキル基を有するアルキル（メタ）アクリレートとしては、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、等の直鎖アルキル（メタ）アクリレート；イソプロピル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、等の分枝鎖アルキル（メタ）アクリレート；シクロプロピル（メタ）アクリレート、シクロブチル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、等の環状アルキル（メタ）アクリレートが挙げられる。これらは、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of alkyl (meth)acrylates having an alkyl group having two or more carbon atoms include linear alkyl (meth)acrylates such as ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and hexyl (meth)acrylate; branched alkyl (meth)acrylates such as isopropyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, isopentyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; and cyclic alkyl (meth)acrylates such as cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, and cyclohexyl (meth)acrylate. These may be used alone or in combination of two or more.
なかでも、炭素数が２以上のアルキル基を有するアルキル（メタ）アクリレートの炭素数は、良好な加工性を得る観点から、アルキル基の炭素数２～１４が好ましく、アルキル基の炭素数２～１０がより好ましい。 Among these, in terms of obtaining good processability, the number of carbon atoms in the alkyl group of alkyl (meth)acrylates having an alkyl group with 2 or more carbon atoms is preferably 2 to 14, and more preferably 2 to 10.
重合体Ａを構成する全構成単位に対する炭素数が２以上のアルキル基を有するアルキル（メタ）アクリレートの単位の割合は、特段の制限はないが、良好な加工性を得る観点から、２０質量％以上１００質量％以下であることが好ましく、２５質量％以上９０質量％以下であることがより好ましく、３０質量％以上８０質量％以下であることが特に好ましい。 The ratio of alkyl (meth)acrylate units having an alkyl group with 2 or more carbon atoms to all structural units constituting polymer A is not particularly limited, but from the viewpoint of obtaining good processability, it is preferably 20% by mass or more and 100% by mass or less, more preferably 25% by mass or more and 90% by mass or less, and particularly preferably 30% by mass or more and 80% by mass or less.
本発明の重合体Ａの構成単位として、さらに、メチル（メタ）アクリレート、芳香族ビニルとビニルニトリルの共重合体、及びビニルハロゲン化物からなる群から選択される１種以上の単位を含んでもよい。重合体Ａを構成する全構成単位に対するこれらの構成単位の割合は、特段の制限はないが、良好な加工性を得る観点から、０質量％以上８０質量％以下であることが好ましく、１０質量％以上７５質量％以下であることがより好ましく、２０質量％以上７０質量％以下であることが特に好ましい。 The structural units of polymer A of the present invention may further include one or more units selected from the group consisting of methyl (meth)acrylate, a copolymer of aromatic vinyl and vinyl nitrile, and a vinyl halide. The ratio of these structural units to all structural units constituting polymer A is not particularly limited, but from the viewpoint of obtaining good processability, it is preferably 0% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 75% by mass or less, and particularly preferably 20% by mass or more and 70% by mass or less.
芳香族ビニルは、例として、スチレン、αーメチルスチレンが挙げられ、ビニルニトリルは、例として、アクリロニトリル、メタクロニトリルが挙げられ、ビニルハロゲン化物は、例として、塩化ビニルが挙げられる。 Examples of aromatic vinyls include styrene and α-methylstyrene, examples of vinyl nitriles include acrylonitrile and methacrylonitrile, and examples of vinyl halides include vinyl chloride.
重合体Ａの構成単位として、メチルメタクリレート単位を含む場合の重合体Ａを構成する全構成単位に対するメチルメタクリレート単位の割合は、特段の制限はないが、良好な加工性を得る観点から、１質量％以上８０質量％以下であることが好ましく、５０質量％以上７５質量％以下であることがより好ましく、５０質量％以上７０質量％以下であることがより好ましい。この場合、重合体Ａを構成する全構成単位に対する炭素数が２以上のアルキル基を有するアルキル（メタ）アクリレート単位の割合は、２０質量％以上９９質量％以下であることが好ましく、２５質量％以上５０質量％以下であることがより好ましく、３０質量％以上５０質量％以下であることがさらに好ましい。 When the polymer A contains methyl methacrylate units as a structural unit, the ratio of the methyl methacrylate units to all structural units constituting the polymer A is not particularly limited, but from the viewpoint of obtaining good processability, it is preferably 1% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 75% by mass or less, and even more preferably 50% by mass or more and 70% by mass or less. In this case, the ratio of the alkyl (meth)acrylate units having an alkyl group having 2 or more carbon atoms to all structural units constituting the polymer A is preferably 20% by mass or more and 99% by mass or less, more preferably 25% by mass or more and 50% by mass or less, and even more preferably 30% by mass or more and 50% by mass or less.
重合体Ａは１種の重合体を使用してもよいし、２種以上の重合体を使用してもよい。 Polymer A may consist of one type of polymer, or two or more types of polymers.
＜重合体Ｂ＞
本発明の重合体Ｂの質量平均分子量は、ラジカル重合開始剤、重合温度、重合時間を変更することで調整でき、良好な加工性を得る観点から、１５０万以下が好ましく、１００万以下がより好ましく、５０万以下が特に好ましく、一方、５万以上が好ましく、１０万以上がさらに好ましく、１２万以上が特に好ましい。
<Polymer B>
The mass average molecular weight of the polymer B of the present invention can be adjusted by changing the radical polymerization initiator, the polymerization temperature, and the polymerization time. From the viewpoint of obtaining good processability, the mass average molecular weight is preferably 1,500,000 or less, more preferably 1,000,000 or less, and particularly preferably 500,000 or less, while it is preferably 50,000 or more, more preferably 100,000 or more, and particularly preferably 120,000 or more.
重合体Ｂのガラス転移温度は、モノマーの仕込みを変えることにより調整でき、７０℃以上が好ましく、８０℃以上がより好ましく、９０℃以上が特に好ましい。 The glass transition temperature of polymer B can be adjusted by changing the monomer charge, and is preferably 70°C or higher, more preferably 80°C or higher, and particularly preferably 90°C or higher.
重合体Ｂの構成単位として、炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位を含んでもよい。 The structural unit of polymer B may contain one or more alkyl (meth)acrylate units having an alkyl group having two or more carbon atoms.
炭素数が２以上のアルキル基を有するアルキル（メタ）アクリレートとしては、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、等の直鎖アルキル（メタ）アクリレート；イソプロピル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、等の分枝鎖アルキル（メタ）アクリレート；シクロプロピル（メタ）アクリレート、シクロブチル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、等の環状アルキル（メタ）アクリレートが挙げられる。これらは、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of alkyl (meth)acrylates having an alkyl group having two or more carbon atoms include linear alkyl (meth)acrylates such as ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and hexyl (meth)acrylate; branched alkyl (meth)acrylates such as isopropyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, isopentyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; and cyclic alkyl (meth)acrylates such as cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, and cyclohexyl (meth)acrylate. These may be used alone or in combination of two or more.
なかでも、アルキル（メタ）アクリレートの炭素数は、良好な加工性を得る観点から、炭素数２～１４が好ましく、炭素数２～１０がより好ましい。 Among these, the number of carbon atoms in the alkyl (meth)acrylate is preferably 2 to 14, and more preferably 2 to 10, from the viewpoint of obtaining good processability.
重合体Ｂを構成する全構成単位に対する炭素数が２以上のアルキル基を有するアルキル（メタ）アクリレートの単位の割合は、特段の制限はないが、良好な粉体取扱い性を得る観点から、０質量％以上４５質量％以下であることが好ましく、０質量％以上２０質量％以下であることがより好ましく、１質量％以上２０質量％以下であること特に好ましい。 The ratio of alkyl (meth)acrylate units having an alkyl group with 2 or more carbon atoms to all structural units constituting polymer B is not particularly limited, but from the viewpoint of obtaining good powder handling properties, it is preferably 0% by mass or more and 45% by mass or less, more preferably 0% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 20% by mass or less.
重合体Ｂの構成単位として、メチル（メタ）アクリレート、芳香族ビニルとビニルニトリルの共重合体、及びビニルハロゲン化物からなる群から選ばれる１種以上の単位を含んでいることが好ましい。重合体Ｂを構成する全構成単位に対するこれらの構成単位の割合は、特段の制限はないが、良好な粉体取扱い性を得る観点から、５５質量％以上１００質量％以下であることが好ましく、８０質量％以上１００質量％以下であることがより好ましく、８０質量％以上９５質量％以下に設定することができる。 As a structural unit of polymer B, it is preferable that the polymer B contains one or more units selected from the group consisting of methyl (meth)acrylate, a copolymer of aromatic vinyl and vinyl nitrile, and a vinyl halide. The ratio of these structural units to all the structural units constituting polymer B is not particularly limited, but from the viewpoint of obtaining good powder handling properties, it is preferably 55% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and can be set to 80% by mass or more and 95% by mass or less.
芳香族ビニルは、例として、スチレン、αーメチルスチレンが挙げられ、ビニルニトリルは、例として、アクリロニトリル、メタクロニトリルが挙げられ、ビニルハロゲン化物は、例として、塩化ビニルが挙げられる。なお、芳香族ビニル、ビニルニトリルの単独重合体は、塩ビ樹脂などに相溶しないので、重合体Ｂの構成成分として用いる際には、芳香族ビニルとビニルニトリルの共重合体とすることが必要である。 Examples of aromatic vinyls include styrene and α-methylstyrene, examples of vinyl nitriles include acrylonitrile and methacrylonitrile, and examples of vinyl halides include vinyl chloride. Note that homopolymers of aromatic vinyls and vinyl nitriles are not compatible with PVC resins, so when using them as components of polymer B, it is necessary to make them into copolymers of aromatic vinyls and vinyl nitrile.
重合体Ｂの構成単位として、メチルメタクリレートの単位を含む場合の重合体Ｂを構成する全構成単位に対するメチルメタクリレートの単位の割合は、良好な加工性と粉体取扱い性を得る観点から、６５質量％以上１００質量％以下であることが好ましく、８０質量％以上１００質量％以下であることがより好ましく、８０質量％以上９５質量％以下に設定することができる。この場合、重合体Ｂを構成する全構成単位に対する炭素数が２以上のアルキル基を有するアルキル（メタ）アクリレートの単位の割合は、０質量％以上３５質量％以下の範囲に設定できる。 When methyl methacrylate units are included as a constituent unit of polymer B, the ratio of methyl methacrylate units to all constituent units constituting polymer B is preferably 65% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, from the viewpoint of obtaining good processability and powder handling properties, and can be set to 80% by mass or more and 95% by mass or less. In this case, the ratio of alkyl (meth)acrylate units having an alkyl group with 2 or more carbon atoms to all constituent units constituting polymer B can be set in the range of 0% by mass or more and 35% by mass or less.
重合体Ｂは１種の重合体を使用してもよいし、２種以上の重合体を使用してもよい。 Polymer B may consist of one type of polymer, or two or more types of polymers.
上述の通り、加工助剤は第三成分を含有していてもよい。第三成分としては、特段の制限はないが、公知のシリカ、タルク、炭酸カルシウム、ハイドロタルサイト、ゼオライト等が挙げられる。加工助剤総質量に対する第三成分の割合は特段の制限はないが、０質量％以上３質量％以下が好ましい。 As mentioned above, the processing aid may contain a third component. There are no particular limitations on the third component, but examples include well-known silica, talc, calcium carbonate, hydrotalcite, zeolite, etc. There are no particular limitations on the ratio of the third component to the total mass of the processing aid, but it is preferably 0% by mass or more and 3% by mass or less.
＜加工助剤の製造方法＞
本発明の加工助剤を得るための重合法は、例えば、乳化重合法、ソープフリー重合法、ミニエマルション重合法、懸濁重合法、等で特に限定はしないが、構造制御の容易性から乳化重合法、ソープフリー重合法が好ましい。
<Method of manufacturing processing aids>
The polymerization method for obtaining the processing aid of the present invention is not particularly limited and may be, for example, an emulsion polymerization method, a soap-free polymerization method, a mini-emulsion polymerization method, a suspension polymerization method, etc., but from the viewpoint of ease of structure control, an emulsion polymerization method and a soap-free polymerization method are preferred.
加工助剤の製造に用いる重合開始剤としては、水溶性、油溶性の単独系もしくはレドックス系の重合開始剤が挙げられる。具体的には、通常の過硫酸塩等の無機系重合開始剤を単独で用いるか、あるいは無機系重合開始剤を、亜硫酸塩、亜硫酸水素塩、チオ硫酸塩等と組み合わせてレドックス系開始剤として用いることもできる。さらにｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、過酸化ベンゾイル、過酸化ラウロイル、等の有機過酸化物、アゾ化合物等を単独で用いるか、あるいはこれらをナトリウムホルムアルデヒドスルホキシレート等と組み合わせてレドックス系開始剤として用いることもできるが、本発明はこれら具体例のみに限定されるものではない。 Polymerization initiators used in the production of processing aids include water-soluble or oil-soluble polymerization initiators of the sole system or redox system. Specifically, inorganic polymerization initiators such as ordinary persulfates can be used alone, or inorganic polymerization initiators can be used in combination with sulfites, hydrogen sulfites, thiosulfates, etc. as redox initiators. Furthermore, organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, and azo compounds can be used alone or in combination with sodium formaldehyde sulfoxylate, etc. as redox initiators, but the present invention is not limited to these specific examples.
例えば乳化重合法で加工助剤を製造する場合、乳化重合法に用いる乳化剤としては、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキルリン酸塩、ジアルキルスルホコハク酸塩、等のアニオン性界面活性剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン酸脂肪エステル、グリセリン脂肪酸エステル、等のノニオン性界面活性剤；アルキルアミン塩、等のカチオン性界面活性剤、等で特に限定はしないが、スルホン酸系のアニオン性界面活性剤が好ましく、アルキルジフェニルエーテルジスルホン酸塩がより好ましい。これらの乳化剤は、単独で用いてもよいし、２種以上を併用してもよい。 For example, when the processing aid is produced by emulsion polymerization, the emulsifiers used in the emulsion polymerization include anionic surfactants such as alkyl sulfonates, alkyl benzene sulfonates, alkyl phosphates, and dialkyl sulfosuccinates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan acid fatty esters, and glycerin fatty acid esters; and cationic surfactants such as alkylamine salts. Although there are no particular limitations, sulfonic acid-based anionic surfactants are preferred, and alkyl diphenyl ether disulfonates are more preferred. These emulsifiers may be used alone or in combination of two or more.
加工助剤を粉体状で回収する方法としては特に制限されないが、例えば乳化重合法により加工助剤を製造する場合には、得られた共重合体のラテックスを冷却し、その後、硫酸、塩酸、等の酸、または塩化アルミニウム、塩化カルシウム、硫酸マグネシウム、硫酸アルミニウム、酢酸カルシウム、等の塩などの電解質により、酸凝固もしくは塩析させて共重合体を沈澱せしめた後、さらに濾過、洗浄、乾燥して加工助剤を得ることができる。また、噴霧乾燥、凍結乾燥等の種々の方法によっても、加工助剤を粉体状で回収することできる。 There are no particular limitations on the method for recovering the processing aid in powder form. For example, when the processing aid is produced by emulsion polymerization, the resulting copolymer latex is cooled, and then the copolymer is precipitated by acid coagulation or salting out with an acid such as sulfuric acid or hydrochloric acid, or an electrolyte such as a salt such as aluminum chloride, calcium chloride, magnesium sulfate, aluminum sulfate, or calcium acetate, and then filtered, washed, and dried to obtain the processing aid. Processing aids can also be recovered in powder form by various methods such as spray drying and freeze drying.
加工助剤の粉体は、ワンポットで製造した共重合体のラテックスを粉体化したものでも良く、別々に製造した異なるラテックスをブレンドして粉体化したものでも良く、別々に粉体化した異なる重合体をブレンドしたものでも良い。 The powdered processing aid may be a powdered copolymer latex produced in one pot, a powdered blend of different latexes produced separately, or a blend of different polymers powdered separately.
加工助剤は、適度な耐ブロッキング性、ゲル化特性及び溶融張力を有することが好ましい。具体的に、樹脂組成物の溶融張力を均質に向上させて、成形加工性を改善したり、加工助剤の粉体流動性を改善して、優れた耐ブロッキング性を実現するために、後述の実施例における評価・測定方法における耐ブロッキング性が「〇」であり、かつ、ゲル化特性の値が７００ｓｅｃ以下であり、かつ、溶融張力が０．２２Ｎ以上であることを同時に満たすことが好ましい。 It is preferable that the processing aid has appropriate blocking resistance, gelling properties, and melt tension. Specifically, in order to improve the melt tension of the resin composition uniformly to improve molding processability, and to improve the powder fluidity of the processing aid to achieve excellent blocking resistance, it is preferable that the blocking resistance is "good" in the evaluation and measurement method in the examples described later, the gelling property value is 700 sec or less, and the melt tension is 0.22 N or more.
＜樹脂組成物＞
樹脂組成物は、少なくとも、マトリックス樹脂と、加工助剤と、を含有する。すなわち、樹脂組成物は、少なくとも、マトリックス樹脂と、重合体Ａと、重合体Ｂと、を含有し、前記重合体Ｂよりも前記重合体Ａが多く含まれる。マトリックス樹脂は熱硬化性樹脂でも熱可塑性樹脂でも良く、特に制限は無いが、好ましくは熱可塑性樹脂であり、より好ましくはハロゲン化ビニル系樹脂であり、特に好ましくは塩化ビニル系樹脂である。
<Resin Composition>
The resin composition contains at least a matrix resin and a processing aid. That is, the resin composition contains at least a matrix resin, a polymer A, and a polymer B, and the polymer A is contained in a larger amount than the polymer B. The matrix resin may be a thermosetting resin or a thermoplastic resin, and is not particularly limited, but is preferably a thermoplastic resin, more preferably a vinyl halide resin, and particularly preferably a vinyl chloride resin.
塩化ビニル系樹脂とは、塩化ビニルモノマーの単独重合体、及び、塩化ビニルモノマーと共重合可能なモノマー群から選ばれた１種以上のモノマーの単位と塩化ビニルモノマーの単位を含む共重合体であり、共重合体中の塩化ビニルモノマーの単位の含有比率は５０質量％以上９９質量％以下が好ましい。 Vinyl chloride resins are homopolymers of vinyl chloride monomers and copolymers containing units of vinyl chloride monomers and units of one or more monomers selected from a group of monomers copolymerizable with vinyl chloride monomers, and the content of vinyl chloride monomer units in the copolymer is preferably 50% by mass or more and 99% by mass or less.
樹脂組成物中、マトリックス樹脂１００質量部に対する重合体Ａと重合体Ｂの合計割合は特段の制限はないが、溶融張力向上のために０．１質量部以上であることが好ましく、０．５質量部以上であることがさらに好ましく、１質量部以上であることが特に好ましく、一方、加工性改良のために３０質量部以下であることが好ましく、１５質量部以下であることがより好ましく、１０質量部以下がさらに好ましく、８質量部以下であることが特に好ましい。 In the resin composition, the total ratio of polymer A and polymer B to 100 parts by mass of the matrix resin is not particularly limited, but in order to improve the melt tension, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more, while in order to improve processability, it is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less.
本発明の樹脂組成物は、必要により、耐衝撃改良剤、安定剤、滑剤、可塑剤、着色剤、充填剤、発泡剤、等のその他の成分を含有していても良い。 The resin composition of the present invention may contain other components such as impact modifiers, stabilizers, lubricants, plasticizers, colorants, fillers, and foaming agents, as necessary.
樹脂組成物中、マトリックス樹脂１００質量部に対するその他の成分の割合は特段の制限はないが、０．１質量％以上であることが好ましく、１質量％以上であることがさらに好ましく、一方、マトリックス樹脂の性質を損なわないために８０質量％以下であることが好ましく、５０質量％以下であることがさらに好ましい。 In the resin composition, the ratio of other components to 100 parts by mass of the matrix resin is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 1% by mass or more, while in order not to impair the properties of the matrix resin, it is preferably 80% by mass or less, and more preferably 50% by mass or less.
樹脂組成物は、各種成分を混合し、バンバリーミキサー、ニーダー、ロール、リボンブレンダ―、ヘンシェルミキサー、等の混練機を用い、例えば１００℃以上２５０℃以下で混練することができる。さらに、混練した樹脂組成物は、押出成形、ブロー成形、射出成型、カレンダー成形、真空成型、等により、適切な形状に成形すれば良い。 The resin composition can be prepared by mixing various components and kneading them using a kneading machine such as a Banbury mixer, kneader, roll, ribbon blender, or Henschel mixer at a temperature of, for example, 100°C or higher and 250°C or lower. The kneaded resin composition can then be molded into an appropriate shape by extrusion molding, blow molding, injection molding, calendar molding, vacuum molding, or the like.
＜ガラス転移温度＞
「ガラス転移温度」（Ｔｇ）は、ガラス状重合体がポリマー鎖の局所的な運動を始める（又は停止する）温度を指す。コポリマーのガラス転移温度は、Ｆｏｘ式（Ｂｕｌｌｅｔｉｎ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｐｈｙｓｉｃａｌ Ｓｏｃｉｅｔｙ，１（３）Ｐａｇｅ１２３（１９５６））により以下の通りに推定され得る。
１／Ｔｇ＝ｗ１／Ｔｇ（１）＋ｗ２／Ｔｇ（２）
コポリマーについては、ｗ１及びｗ２は、２つのコモノマーの重量分率を指し、Ｔｇ（１）及びＴｇ（２）は、モノマーから作製された２つの対応するホモポリマーのガラス転移温度を指す。３つ以上のモノマーを含む重合体については、追加の項が加えられる（ｗｎ／Ｔｇ（ｎ））。ホモポリマーのガラス転移温度は、例えば“Ｐｏｌｙｍｅｒ Ｈａｎｄｂｏｏｋ，”ｅｄｉｔｅｄ ｂｙ Ｊ．Ｂｒａｎｄｒｕｐ ａｎｄ Ｅ．Ｈ．Ｉｍｍｅｒｇｕｔ，Ｉｎｔｅｒｓｃｉｅｎｃｅ Ｐｕｂｌｉｓｈｅｒｓで見ることができる。
<Glass transition temperature>
"Glass transition temperature" (Tg) refers to the temperature at which a glassy polymer begins (or stops) localized motion of the polymer chains. The glass transition temperature of a copolymer can be estimated by the Fox equation (Bulletin of the American Physical Society, 1(3) Page 123 (1956)) as follows:
1/Tg=w1/Tg(1)+w2/Tg(2)
For copolymers, w1 and w2 refer to the weight fractions of the two comonomers, and Tg(1) and Tg(2) refer to the glass transition temperatures of the two corresponding homopolymers made from the monomers. For polymers containing three or more monomers, additional terms are added (wn/Tg(n)). The glass transition temperatures of homopolymers can be found, for example, in "Polymer Handbook," edited by J. Brandrup and E. H. Immergut, Interscience Publishers.
＜加工助剤の分析＞
加工助剤は以下に示す条件で、Ｇｒａｄｉｅｎｔ Ｐｏｌｙｍｅｒ Ｅｌｕｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ（ＧＰＥＣ）によって分離し、共重合組成と重量平均分子量を測定することができる。
［ＧＰＥＣ条件］
装置：アジレント・テクノロジー社製 Ｉｎｆｉｎｉｔｙ１２６０
検出器：サーモフィッシャーサイエンティフィック社製 Ｃｏｒｏｎａ ＶｅｏＲＳ カラム：ＴＳＫｇｅｌ ＯＤＳ－１００Ｖ（４．６×１５０ｍｍ、５μｍ）
カラム温度：４０℃
移動相：ＡＴＮ／ＴＨＦ＝１００／０→０／１００（１０ｍｉｎ)→０／１００（１５ｍｉｎ）
流量：１．０ｍｌ／ｍｉｎ
濃度：１０００ｐｐｍ（ＴＨＦ ＢＨＴ含有）
注入量：１μｌ
<Analysis of processing aids>
The processing aid can be separated by gradient polymer elution chromatography (GPEC) under the conditions shown below, and the copolymer composition and weight average molecular weight can be measured.
[GPEC conditions]
Apparatus: Agilent Technologies Infinity 1260
Detector: Corona VeoRS manufactured by Thermo Fisher Scientific Column: TSKgel ODS-100V (4.6 x 150 mm, 5 μm)
Column temperature: 40°C
Mobile phase: ATN/THF=100/0 → 0/100 (10 min) → 0/100 (15 min)
Flow rate: 1.0ml/min
Concentration: 1000ppm (THF BHT included)
Injection volume: 1 μl
＜共重合組成測定方法＞
重合体の共重合組成は以下の条件で、Ｐｙｒｏｌｙｓｉｓ Ｇａｓ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ－Ｍａｓｓ Ｓｐｅｃｔｒｏｍｅｔｒｙ（ＰＹ－ＧＣ／ＭＳ）と、Ｎｕｃｌｅａｒ Ｍａｇｎｅｔｉｃ Ｒｅｓｏｎａｎｃｅ（１Ｈ－ＮＭＲ）によって同定する。
［ＰＹ－ＧＣ／ＭＳ条件］
測定装置：ＧＣ－７８９０Ａ、ＭＳＤ－５９７５Ｃ、ＥＧＡ／ＰＹ－２０２０Ｄ
測定条件：ＰＹ／ＩＦ ６００℃／３２０℃
カラム：ＵＡ－５（３０ｍ、０．２５ｍｍ、０．２５μｍ）
キャリアガス：ヘリウム（１ｍＬ／ｍｉｎ）
検出器：ＭＡＤ（ＥＩ）
オーブン温度：４０℃（２ｍｉｎ）→２０℃／ｍｉｎで昇温→３２０℃（５ｍｉｎ）
注入口温度：３２０℃
トランスファー温度：３２０℃
質量スペクトル範囲：２０～１０００
スプリット比：５０／１
<Method for measuring copolymer composition>
The copolymer composition of the polymer is identified by pyrolysis gas chromatography-mass spectrometry (PY-GC/MS) and nuclear magnetic resonance ( 1 H-NMR) under the following conditions.
[PY-GC/MS conditions]
Measuring device: GC-7890A, MSD-5975C, EGA/PY-2020D
Measurement conditions: PY/IF 600°C/320°C
Column: UA-5 (30 m, 0.25 mm, 0.25 μm)
Carrier gas: Helium (1 mL/min)
Detector: MAD (EI)
Oven temperature: 40°C (2 min) → 20°C/min heating rate → 320°C (5 min)
Inlet temperature: 320℃
Transfer temperature: 320°C
Mass spectrum range: 20-1000
Split ratio: 50/1
［１Ｈ－ＮＭＲ条件］
装置：日本電子社製 ＪＮＭ ＥＸ－２７０
溶媒：重クロロホルム（７．２６ｐｐｍ）
濃度：２０ｍｇ／６５ｍｌ
温度：２３℃
積算：６４回
[ 1H -NMR conditions]
Equipment: JNM EX-270 manufactured by JEOL Ltd.
Solvent: deuterated chloroform (7.26 ppm)
Concentration: 20mg/65ml
Temperature: 23°C
Total: 64 times
＜重量平均分子量測定方法＞
重合体の重量平均分子量は以下の条件で、Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ（ＧＰＣ）によって同定する。
［ＧＰＣ条件］
装置：東ソー製 ＨＬＣ－８３２０
分離カラム：ＴＳＫ－ｇｕａｒｄｃｏｌｕｍｎ ＨＨＲ（３０） （７．５ｍｍφ×７５ｍｍ）と、ＴＳＫ－ＧＥＬ ＧＭＨＨＲ－Ｈ（２０） （２０μｍ、７．８ｍｍφ×３００ｍｍ）を直列に連結する。
カラム温度：４０℃
溶離液：特級ＴＨＦ（安定剤含有）
濃度：１０ｍｇ／１０ｍｌ
流速：０．６００ｍｌ／ｍｉｎ
注入量：１０μｌ
検出器：ＲＩ（示差屈折計）
検量線：単分散ポリスチレン
内部標準：アンテージＷ４００
<Weight average molecular weight measurement method>
The weight average molecular weight of the polymer is determined by gel permeation chromatography (GPC) under the following conditions.
[GPC conditions]
Equipment: Tosoh HLC-8320
Separation column: TSK-guard column HHR (30) (7.5 mmφ×75 mm) and TSK-GEL GMHHR-H (20) (20 μm, 7.8 mmφ×300 mm) are connected in series.
Column temperature: 40°C
Eluent: THF (contains stabilizer)
Concentration: 10mg/10ml
Flow rate: 0.600ml/min
Injection volume: 10 μl
Detector: RI (differential refractometer)
Calibration curve: Monodisperse polystyrene Internal standard: Antage W400
＜加工助剤の耐ブロッキング性の評価方法＞
加工助剤２０ｇを計量し、直径６５ｍｍの円柱状の型に入れ、さらに型の上に、重りとして、５ｋｇの錘を置いた状態で、６０℃で２時間加熱する。加熱後に円柱状に固まった加工助剤の試験片を取り出し、１２メッシュの篩に乗せて、ミクロ型電磁振動ふるい振とう器（筒井理化学器械製、Ｍ－２）のダイヤル１０で振動を１０分間与える。試験後に篩の上に残った試験片の質量を測定し、元の試験片に対する質量の減少率を求める。質量減少率２０％を基準として、減少率２０％以上のサンプルを耐ブロッキング性が良好として「○」とし、減少率２０％未満のサンプルを耐ブロッキング性が不良として「×」として評価する。
<Method for evaluating blocking resistance of processing aids>
20 g of the processing aid is weighed out and placed in a cylindrical mold with a diameter of 65 mm, and heated at 60° C. for 2 hours with a 5 kg weight placed on the mold as a weight. After heating, a test piece of the processing aid that has solidified into a cylindrical shape is taken out and placed on a 12 mesh sieve, and vibration is applied for 10 minutes using dial 10 of a micro-type electromagnetic vibration sieve shaker (Tsutsui Rikagaku Kikai, M-2). After the test, the mass of the test piece remaining on the sieve is measured, and the mass reduction rate relative to the original test piece is calculated. Based on a mass reduction rate of 20%, samples with a reduction rate of 20% or more are evaluated as having good blocking resistance and are marked with "○", and samples with a reduction rate of less than 20% are evaluated as having poor blocking resistance and are marked with "×".
＜樹脂組成物のゲル化特性の評価方法＞
１６０℃に加熱したプラスチコーダー（ブラベンダー社製）に、塩化ビニル樹脂組成物を６０ｇ充填し、３分間保持した後、温度１６０℃、回転数３０ｒｐｍの条件にてゲル化特性を観察する。混練の開始後、トルクが３０Ｎ・ｍを超えるまでに要した時間をゲル化時間として読み取った。なお、ゲル化時間が短いほど、加工助剤が均質に分散して加工性が良好であることを意味し、例えば、発泡押出成形で均質な外観の成形品を得るためには、ゲル化時間が７００ｓｅｃ以下であることが好ましく、６８０ｓｅｃ以下であることがより好ましく、ゲル化時間が６７５ｓｅｃ以下であることがさらに好ましい。
<Method for evaluating gelling properties of resin composition>
60 g of the vinyl chloride resin composition is filled into a Plasticorder (manufactured by Brabender) heated to 160°C, and after holding for 3 minutes, the gelation characteristics are observed under the conditions of a temperature of 160°C and a rotation speed of 30 rpm. The time required for the torque to exceed 30 N·m after the start of kneading is read as the gelation time. The shorter the gelation time, the more homogeneously the processing aid is dispersed and the better the processability. For example, in order to obtain a molded product with a homogeneous appearance by foam extrusion molding, the gelation time is preferably 700 sec or less, more preferably 680 sec or less, and even more preferably 675 sec or less.
＜樹脂組成物の溶融張力の評価方法＞
１８５℃に加熱した直径８インチの熱ロールで、塩化ビニル樹脂組成物２５０ｇを３分間混練してロールシートを作製し、ロールシートを短冊状（５ｍｍ×８０ｍｍ×０．５ｍｍｔ）に切断して試験片を作製する。試験片を１９５℃に設定したツインキャピラリーレオメーター（ＲＯＳＡＮＤ製、ＲＨ－７）に投入し、５分間予熱を行い、ピストン速度８．８９ｍｍ／ｍｉｎで押し出して、６ｍ／ｍｉｎで巻き取りながら溶融張力を測定した。溶融張力が高いと、発泡成形においては、発泡セルの構造が固定され、均質で発泡倍率の高い成形品が得られるが、良好な発泡倍率の成形品を得るためには、溶融張力は、０．２２Ｎ以上であることが好ましく、０．２４Ｎ以上であることがより好ましく、０．２６Ｎ以上であることがさらに好ましい。
<Method for evaluating melt tension of resin composition>
250 g of the vinyl chloride resin composition was kneaded for 3 minutes with a heated roll of 8 inches in diameter heated to 185 ° C. to prepare a roll sheet, and the roll sheet was cut into strips (5 mm × 80 mm × 0.5 mmt) to prepare a test piece. The test piece was placed in a twin capillary rheometer (manufactured by ROSAND, RH-7) set at 195 ° C., preheated for 5 minutes, extruded at a piston speed of 8.89 mm / min, and wound up at 6 m / min while measuring the melt tension. When the melt tension is high, the structure of the foam cells is fixed in the foam molding, and a homogeneous molded product with a high expansion ratio can be obtained, but in order to obtain a molded product with a good expansion ratio, the melt tension is preferably 0.22 N or more, more preferably 0.24 N or more, and even more preferably 0.26 N or more.
（製造例１）
（樹脂組成物の製造）
平均重合度１０００の塩化ビニル樹脂（信越化学工業株式会社製、「ＴＫ－１０００」）１００質量部、Ｃａ－Ｚｎ系安定剤（日東化成工業株式会社製、「ＨＴ－５４７Ａ」）４質量部、滑剤としてエステル系滑剤（エメリーオレオケミカルズジャパン株式会社製、「ＬＯＸＩＯＬ ＶＰＮ９６３」）０．５質量部、エステル系滑剤（エメリーオレオケミカルズジャパン株式会社製、「ＬＯＸＩＯＬ Ｇ６０」）０．５質量部、充填剤として炭酸カルシウム（白石工業株式会社製、「μ―ＰＯＷＤＥＲ ３Ｓ」）５質量部、酸化チタン（石原産業株式会社製、「Ｒ－８３０」）４．５質量部を、ヘンシェルミキサーで混合し、１１０℃まで昇温させて、塩化ビニル樹脂組成物を得た。
(Production Example 1)
(Production of resin composition)
100 parts by mass of a vinyl chloride resin having an average degree of polymerization of 1000 (manufactured by Shin-Etsu Chemical Co., Ltd., "TK-1000"), 4 parts by mass of a Ca-Zn-based stabilizer (manufactured by Nitto Kasei Kogyo Co., Ltd., "HT-547A"), 0.5 parts by mass of an ester-based lubricant (manufactured by Emery Oleochemicals Japan Co., Ltd., "LOXIOL VPN963") as a lubricant, 0.5 parts by mass of an ester-based lubricant (manufactured by Emery Oleochemicals Japan Co., Ltd., "LOXIOL G60") as a lubricant, 5 parts by mass of calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., "μ-POWDER 3S") as a filler, and 4.5 parts by mass of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., "R-830") were mixed in a Henschel mixer and heated to 110°C to obtain a vinyl chloride resin composition.
（実施例１）
（加工助剤の製造）
攪拌機及び環流冷却器付きの反応容器にイオン交換水１１５質量部を仕込み、そこに無水炭酸ナトリウム０．１質量部、メタクリル酸メチル（ＭＭＡ）５４．５質量部、アクリル酸－ｎ－ブチル（ＢＡ）３０質量部を加えて、反応容器内を窒素で置換した。その後、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム（花王株式会社製、「ぺレックスＳＳ－Ｌ」）１．７質量部を加え、攪拌下で反応容器を５０℃まで昇温し、重合開始剤として過硫酸カリウム０．１３質量部を仕込み、重合反応を開始させ、４時間加熱攪拌して重合を終了し、重合体Ａを含むエマルジョンを得た。
得られたエマルジョンを８０℃まで昇温し、過硫酸カリウム０．０４質量部を追加した。その後、メタクリル酸メチル（ＭＭＡ）１５．５質量部とオクチルメルカプタン０．００８質量部の混合液を３０分かけて滴下し、滴下後に１時間保持して、重合体Ａと重合体Ｂを含むエマルジョンを得た。
得られたエマルジョンを熱風の入口温度が１３５℃の条件で噴霧乾燥し、加工助剤の粉体を得た。
得られた加工助剤を分離して、共重合組成と重量平均分子量（Ｍｗ）を測定したところ、Ｍｗ＝４６０万、ＭＭＡ／ＢＡ＝６５質量％／３５質量％の重合体と、Ｍｗ＝４９万、ＭＭＡ＝１００質量％の重合体を、８５質量％：１５質量％の割合で含む加工助剤であった。
Example 1
(Manufacturing of processing aids)
A reaction vessel equipped with a stirrer and a reflux condenser was charged with 115 parts by mass of ion-exchanged water, to which 0.1 parts by mass of anhydrous sodium carbonate, 54.5 parts by mass of methyl methacrylate (MMA), and 30 parts by mass of n-butyl acrylate (BA) were added, and the atmosphere in the reaction vessel was replaced with nitrogen. Thereafter, 1.7 parts by mass of sodium alkyl diphenyl ether disulfonate (manufactured by Kao Corporation, "Pelex SS-L") was added as an emulsifier, and the reaction vessel was heated to 50°C under stirring, and 0.13 parts by mass of potassium persulfate was charged as a polymerization initiator to initiate the polymerization reaction, and the polymerization was terminated by heating and stirring for 4 hours, to obtain an emulsion containing polymer A.
The obtained emulsion was heated to 80° C., and 0.04 parts by mass of potassium persulfate was added. Then, a mixed liquid of 15.5 parts by mass of methyl methacrylate (MMA) and 0.008 parts by mass of octyl mercaptan was added dropwise over 30 minutes, and the mixture was held for 1 hour after the dropwise addition to obtain an emulsion containing polymer A and polymer B.
The resulting emulsion was spray-dried under conditions of an inlet hot air temperature of 135° C. to obtain a powder of the processing aid.
The obtained processing aid was separated, and the copolymer composition and weight average molecular weight (Mw) were measured. It was found to be a processing aid containing a polymer with Mw = 4,600,000 and MMA/BA = 65% by mass/35% by mass, and a polymer with Mw = 490,000 and MMA = 100% by mass, in a ratio of 85% by mass:15% by mass.
（加工助剤および樹脂組成物の評価）
得られた加工助剤の粉体について前述の加工助剤の耐ブロッキング性の評価方法にて耐ブロッキング性を評価した。また、製造例１で得られた塩化ビニル樹脂組成物１１４．５質量部に対して得られた加工助剤１質量部を加えてゲル化特性を評価した。さらに製造例１で得られた塩化ビニル樹脂組成物１１４．５質量部に対して得られた加工助剤７質量部を加えて溶融張力を評価した。これらの結果を表１に示す。
(Evaluation of Processing Aids and Resin Compositions)
The obtained powder of the processing aid was evaluated for blocking resistance by the above-mentioned method for evaluating the blocking resistance of processing aids. In addition, 1 part by mass of the obtained processing aid was added to 114.5 parts by mass of the vinyl chloride resin composition obtained in Production Example 1 to evaluate gelling properties. Furthermore, 7 parts by mass of the obtained processing aid was added to 114.5 parts by mass of the vinyl chloride resin composition obtained in Production Example 1 to evaluate melt tension. These results are shown in Table 1.
（実施例２～１２、比較例１～４）
重合体の組成及び分子量を表１に示すように変更した以外は、実施例１と同様にして、ゲル化特性と溶融張力の測定によって加工性、及び耐ブロッキング性の試験によって粉体流動性の評価を行った。結果を表１に示す。表１中の「ＡＮ」はアクリロニトリル、「Ｓｔ」はスチレン、「ＢＭＡ」はブチルメタクリレートを示し、重量平均分子量（Ｍｗ）の「ｋ」は１０３を示す。
(Examples 2 to 12, Comparative Examples 1 to 4)
Except for changing the composition and molecular weight of the polymer as shown in Table 1, the processability was evaluated by measuring the gelling characteristics and melt tension, and the powder flowability was evaluated by testing the blocking resistance in the same manner as in Example 1. The results are shown in Table 1. In Table 1, "AN" stands for acrylonitrile, "St" stands for styrene, "BMA" stands for butyl methacrylate, and "k" in the weight average molecular weight (Mw) stands for 103 .
表１の結果より、各実施例１～１２で得られた加工助剤および樹脂組成物は、耐ブロッキング性が「〇」であり、かつ、ゲル化特性の値が７００ｓｅｃ以下であり、さらには、溶融張力が０．２２Ｎ以上であることを満たしていることから、溶融張力が高く、ゲル化時間が短くて、加工性が良好でありながら、粉体流動性が良好で優れた耐ブロッキング性を有することが示された。 The results in Table 1 show that the processing aids and resin compositions obtained in Examples 1 to 12 had a blocking resistance of "good," a gelling property value of 700 sec or less, and a melt tension of 0.22 N or more. This indicates that the processing aids and resin compositions obtained in Examples 1 to 12 have high melt tension, short gelling time, and good processability, as well as good powder fluidity and excellent blocking resistance.
Claims (14)
前記重合体Ａの構成単位として、
ブチル（メタ）アクリレートの単位を少なくとも含み、
さらにメチル（メタ）アクリレートの単位、芳香族ビニルとビニルニトリルの共重合体の単位、及びビニルハロゲン化物の単位からなる群から選択される１種以上の単位を任意で含有し、
前記重合体Ａを構成する全構成単位に対する、ブチル（メタ）アクリレートの単位の割合が２０質量％以上１００質量％以下、メチル（メタ）アクリレートの単位、芳香族ビニルとビニルニトリルの共重合体の単位、及びビニルハロゲン化物の単位の合計割合が０質量％以上８０質量％以下であり、
前記重合体Ｂの構成単位として、
メチルメタクリレートの単位及び芳香族ビニルとビニルニトリルの共重合体の単位の少なくとも一方を含み、さらに任意で炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位を含み、
前記重合体Ｂを構成する全構成単位に対する、メチルメタクリレートの単位及び芳香族ビニルとビニルニトリルの共重合体の単位の合計割合が５５質量％以上１００質量％以下、炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位の割合が０質量％以上４５質量％以下である、加工助剤。 A processing aid comprising: a polymer A having a weight-average molecular weight of 3,000,000 or more and a glass transition temperature of 50° C. or less; and a polymer B having a weight-average molecular weight of 1,500,000 or less and a glass transition temperature of 70° C. or more, wherein the polymer A is contained in a larger amount than the polymer B ;
As the structural unit of the polymer A,
Contains at least a unit of butyl (meth)acrylate,
further optionally containing one or more units selected from the group consisting of methyl (meth)acrylate units, copolymer units of aromatic vinyl and vinyl nitrile, and vinyl halide units;
a ratio of butyl (meth)acrylate units to all structural units constituting the polymer A is 20% by mass or more and 100% by mass or less, and a total ratio of methyl (meth)acrylate units, units of a copolymer of aromatic vinyl and vinyl nitrile, and units of a vinyl halide is 0% by mass or more and 80% by mass or less,
As the structural unit of the polymer B,
The copolymer comprises at least one of a methyl methacrylate unit and a copolymer unit of an aromatic vinyl and a vinyl nitrile, and optionally further comprises one or more alkyl (meth)acrylate units having an alkyl group having two or more carbon atoms;
A processing aid in which the total proportion of methyl methacrylate units and aromatic vinyl/vinyl nitrile copolymer units relative to all structural units constituting the polymer B is 55% by mass or more and 100% by mass or less, and the proportion of one or more alkyl (meth)acrylate units having an alkyl group having two or more carbon atoms is 0% by mass or more and 45% by mass or less .
前記重合体Ａの構成単位として、As the structural unit of the polymer A,
ブチル（メタ）アクリレートの単位とメチルメタクリレートの単位を含み、Contains butyl (meth)acrylate units and methyl methacrylate units,
前記重合体Ａを構成する全構成単位に対する、ブチル（メタ）アクリレートの単位の割合が２０質量％以上９９質量％以下、メチルメタクリレートの単位の割合が１質量％以上８０質量％以下であり、a ratio of butyl (meth)acrylate units to all structural units constituting the polymer A is 20% by mass or more and 99% by mass or less, and a ratio of methyl methacrylate units is 1% by mass or more and 80% by mass or less,
前記重合体Ｂの構成単位として、As the structural unit of the polymer B,
メチルメタクリレートの単位及び芳香族ビニルとビニルニトリルの共重合体の単位の少なくとも一方を含み、さらに任意で炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位を含み、The copolymer comprises at least one of a methyl methacrylate unit and a copolymer unit of an aromatic vinyl and a vinyl nitrile, and optionally further comprises one or more alkyl (meth)acrylate units having an alkyl group having two or more carbon atoms;
前記重合体Ｂを構成する全構成単位に対する、メチルメタクリレートの単位及び芳香族ビニルとビニルニトリルの共重合体の単位の合計割合が５５質量％以上１００質量％以下、炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位の割合が０質量％以上４５質量％以下である、加工助剤。A processing aid in which the total proportion of methyl methacrylate units and aromatic vinyl/vinyl nitrile copolymer units relative to all structural units constituting the polymer B is 55% by mass or more and 100% by mass or less, and the proportion of one or more alkyl (meth)acrylate units having an alkyl group having two or more carbon atoms is 0% by mass or more and 45% by mass or less.
前記重合体Ａの構成単位として、
ブチル（メタ）アクリレートの単位を少なくとも含み、
さらにメチル（メタ）アクリレートの単位、芳香族ビニルとビニルニトリルの共重合体の単位、及びビニルハロゲン化物の単位からなる群から選択される１種以上の単位を任意で含有し、
前記重合体Ａを構成する全構成単位に対する、ブチル（メタ）アクリレートの単位の割合が２０質量％以上１００質量％以下、メチル（メタ）アクリレートの単位、芳香族ビニルとビニルニトリルの共重合体の単位、及びビニルハロゲン化物の単位の合計割合が０質量％以上８０質量％以下であり、
前記重合体Ｂの構成単位として、
メチルメタクリレートの単位及び芳香族ビニルとビニルニトリルの共重合体の単位の少なくとも一方を含み、さらに任意で炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位を含み、
前記重合体Ｂを構成する全構成単位に対する、メチルメタクリレートの単位及び芳香族ビニルとビニルニトリルの共重合体の単位の合計割合が５５質量％以上１００質量％以下、炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位の割合が０質量％以上４５質量％以下である、樹脂組成物。 A resin composition comprising: a polymer A having a weight-average molecular weight of 3,000,000 or more and a glass transition temperature of 50° C. or less; a polymer B having a weight-average molecular weight of 1,500,000 or less and a glass transition temperature of 70° C. or more; and a matrix resin, the polymer A being contained in a larger amount than the polymer B,
As the structural unit of the polymer A,
Contains at least a unit of butyl (meth)acrylate,
further optionally containing one or more units selected from the group consisting of methyl (meth)acrylate units, copolymer units of aromatic vinyl and vinyl nitrile, and vinyl halide units;
a ratio of butyl (meth)acrylate units to all structural units constituting the polymer A is 20% by mass or more and 100% by mass or less, and a total ratio of methyl (meth)acrylate units, units of a copolymer of aromatic vinyl and vinyl nitrile, and units of a vinyl halide is 0% by mass or more and 80% by mass or less,
As the structural unit of the polymer B,
The copolymer contains at least one of a methyl methacrylate unit and a copolymer unit of an aromatic vinyl and a vinyl nitrile, and optionally further contains one or more alkyl (meth)acrylate units having an alkyl group having two or more carbon atoms;
A resin composition, wherein the total ratio of methyl methacrylate units and aromatic vinyl/vinyl nitrile copolymer units to all structural units constituting the polymer B is 55% by mass or more and 100% by mass or less, and the ratio of one or more alkyl (meth)acrylate units having an alkyl group having 2 or more carbon atoms is 0% by mass or more and 45% by mass or less .
前記重合体Ａの構成単位として、As the structural unit of the polymer A,
ブチル（メタ）アクリレートの単位とメチルメタクリレートの単位を含み、Contains butyl (meth)acrylate units and methyl methacrylate units,
前記重合体Ａを構成する全構成単位に対する、ブチル（メタ）アクリレートの単位の割合が２０質量％以上９９質量％以下、メチルメタクリレートの単位の割合が１質量％以上８０質量％以下であり、a ratio of butyl (meth)acrylate units to all structural units constituting the polymer A is 20% by mass or more and 99% by mass or less, and a ratio of methyl methacrylate units is 1% by mass or more and 80% by mass or less,
前記重合体Ｂの構成単位として、As the structural unit of the polymer B,
メチルメタクリレートの単位及び芳香族ビニルとビニルニトリルの共重合体の単位の少なくとも一方を含み、さらに任意で炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位を含み、The copolymer comprises at least one of a methyl methacrylate unit and a copolymer unit of an aromatic vinyl and a vinyl nitrile, and optionally further comprises one or more alkyl (meth)acrylate units having an alkyl group having two or more carbon atoms;
前記重合体Ｂを構成する全構成単位に対する、メチルメタクリレートの単位及び芳香族ビニルとビニルニトリルの共重合体の単位の合計割合が５５質量％以上１００質量％以下、炭素数が２以上のアルキル基を有する１種以上のアルキル（メタ）アクリレートの単位の割合が０質量％以上４５質量％以下である、樹脂組成物。A resin composition, wherein the total ratio of methyl methacrylate units and aromatic vinyl/vinyl nitrile copolymer units to all structural units constituting the polymer B is 55% by mass or more and 100% by mass or less, and the ratio of one or more alkyl (meth)acrylate units having an alkyl group having 2 or more carbon atoms is 0% by mass or more and 45% by mass or less.
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| JP2001031826A (en) | 1999-05-19 | 2001-02-06 | Mitsubishi Rayon Co Ltd | Processing aid, vinyl chloride resin composition using the same, and method for producing molded article using the same |
| JP2001323006A (en) | 2000-05-12 | 2001-11-20 | Rohm & Haas Co | Plastic additive polymer composition |
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