WO2022113906A1 - アイオノマー樹脂 - Google Patents
アイオノマー樹脂 Download PDFInfo
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- WO2022113906A1 WO2022113906A1 PCT/JP2021/042630 JP2021042630W WO2022113906A1 WO 2022113906 A1 WO2022113906 A1 WO 2022113906A1 JP 2021042630 W JP2021042630 W JP 2021042630W WO 2022113906 A1 WO2022113906 A1 WO 2022113906A1
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- WIPO (PCT)
- Prior art keywords
- carboxylic acid
- unit
- mol
- ionomer resin
- resin
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 348
- 239000011347 resin Substances 0.000 title claims abstract description 348
- 229920000554 ionomer Polymers 0.000 title claims abstract description 183
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000005977 Ethylene Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 29
- -1 polyethylene Polymers 0.000 claims abstract description 29
- 150000001735 carboxylic acids Chemical group 0.000 claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims abstract description 12
- 229920000573 polyethylene Polymers 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims abstract 8
- 229920001577 copolymer Polymers 0.000 claims description 59
- 239000005340 laminated glass Substances 0.000 claims description 59
- 239000011521 glass Substances 0.000 claims description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 44
- 239000011342 resin composition Substances 0.000 claims description 29
- 239000011229 interlayer Substances 0.000 claims description 28
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 98
- 238000000034 method Methods 0.000 description 55
- 150000001733 carboxylic acid esters Chemical group 0.000 description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 239000000047 product Substances 0.000 description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 239000010410 layer Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 23
- 239000003963 antioxidant agent Substances 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 19
- 238000004040 coloring Methods 0.000 description 17
- 238000010583 slow cooling Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000007127 saponification reaction Methods 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 239000012046 mixed solvent Substances 0.000 description 13
- 230000003472 neutralizing effect Effects 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 230000007774 longterm Effects 0.000 description 12
- 230000006866 deterioration Effects 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 238000002788 crimping Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000001491 aromatic compounds Chemical class 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000011088 calibration curve Methods 0.000 description 5
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000010094 polymer processing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000001565 benzotriazoles Chemical class 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 3
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 235000021355 Stearic acid Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
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- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
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- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
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- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 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
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical group [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 2
- 239000008117 stearic acid Substances 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
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- ONDSBJMLAHVLMI-UHFFFAOYSA-N trimethylsilyldiazomethane Chemical compound C[Si](C)(C)[CH-][N+]#N ONDSBJMLAHVLMI-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- UDYXMTORTDACTG-UHFFFAOYSA-N 1,1,3-tributylthiourea Chemical compound CCCCNC(=S)N(CCCC)CCCC UDYXMTORTDACTG-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical class ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- YLMXNQPOOVZIHK-UHFFFAOYSA-N 1,3-bis[3-(dimethylamino)propyl]thiourea Chemical compound CN(C)CCCNC(=S)NCCCN(C)C YLMXNQPOOVZIHK-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
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- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Definitions
- the present invention relates to an ionomer resin capable of forming a resin sheet that can be used as an interlayer film for laminated glass, a resin composition containing the ionomer resin, a resin sheet containing the ionomer resin or the resin composition, and the resin sheet. With respect to laminated glass having.
- Ionomer resin which is a neutralized product of ethylene / unsaturated carboxylic acid copolymer, is used as an interlayer film of laminated glass because of its excellent transparency and adhesiveness to glass (for example, Patent Document 1).
- Patent Document 1 the required performance for laminated glass has increased, and even for ionomer resin, it maintains high transparency regardless of the manufacturing conditions of laminated glass, has less coloring and is superior in appearance, and even in a high temperature environment. It has been required to have high independence and to have high adhesive strength even when laminated glass is bonded at a lower temperature than before.
- Patent Document 2 describes an ionomer resin in which 5 to 15% by mass of an ⁇ , ⁇ -unsaturated carboxylic acid derivative is introduced as a third component into an ethylene / unsaturated carboxylic acid copolymer. Ionomer resin has improved transparency.
- the ionomer resin as in Patent Document 2 does not have sufficient high transparency, low coloring property, and high independence in a high temperature environment required for an interlayer film of laminated glass. I understood it. Further, an ionomer resin as in Patent Document 2 cannot exhibit sufficient adhesive strength with glass when it is bonded to glass at a lower temperature than before, and has a low elastic modulus after a long period of time, so that it is high. It was also found that the strength could not be maintained.
- an object of the present invention is to have excellent transparency and self-supporting property in a high temperature environment, low coloring property, sufficient adhesiveness to glass even when bonded to laminated glass at a lower temperature than before, and ,
- An ionomer resin capable of forming a resin sheet capable of maintaining high strength even after a long period of time, a resin composition containing the ionomer resin, the ionomer resin or a resin sheet containing the resin composition, and the resin sheet.
- the purpose is to provide laminated glass having.
- the present inventor has an ionomer containing a carboxylic acid ester unit (A), a carboxylic acid unit (B), a carboxylic acid neutralizer unit (C) and an ethylene unit (D).
- the content of the carboxylic acid ester unit (A) is 0.01 to 1.8 mol%, and the total content of these units is 6 to 10 mol%, which is a number average in terms of a specific polyethylene.
- the present invention includes the following.
- the content of the carboxylic acid ester unit (A) is 0.01 to 1.8 mol%, and the carboxylic acid ester unit (A) and the carboxylic acid are based on all the monomer units constituting the ionomer resin.
- the total content of the unit (B) and the carboxylic acid neutralizer unit (C) is 6 to 10 mol%.
- the molecular weight obtained from the integrated molecular weight distribution curve is 2,500 or less.
- the ionomer resin has a ratio of low molecular weight components of 2.6 to 4.0% by mass and a number average molecular weight of 8,000 to 14,000 g / mol. [2] The ionomer resin according to [1], wherein the content of the carboxylic acid neutralized product unit (C) is 0.1 to 3.0 mol%.
- the content of the carboxylic acid ester unit contained in the ethylene-carboxylic acid ester copolymer (X) is 6 to 10 mol based on all the monomer units constituting the ethylene-carboxylic acid ester copolymer.
- % The method for producing an ionomer resin according to any one of [1] to [4].
- [6] A resin composition containing 90% by mass or more of the ionomer resin according to any one of [1] to [4] with respect to the mass of the resin composition.
- [7] A resin sheet containing the ionomer resin according to any one of [1] to [4] or the resin composition according to [6].
- the ionomer resin of the present invention has excellent transparency, self-supporting property in a high temperature environment, low coloring property, has sufficient adhesiveness to glass even when bonded to glass at a lower temperature than before, and has a long length. It is possible to form a resin sheet that can maintain high strength over time. Therefore, it can be suitably used as an interlayer film for laminated glass.
- the ionomer resin of the present invention contains a carboxylic acid ester unit (A), a carboxylic acid unit (B), a carboxylic acid neutralizer unit (C) and an ethylene unit (D), and all the monomers constituting the ionomer resin.
- the content of the carboxylic acid ester unit (A) is 0.01 to 1.8 mol% based on the unit, and the carboxylic acid ester unit (A), the carboxylic acid unit (B), and the carboxylic acid neutralization.
- total content of the substance unit (C) (hereinafter, may be referred to as “total content of units (A) to (C)”) is 6 to 10 mol%, and is contained in the carboxylic acid unit (B) and the carboxylic acid.
- total content of units (A) to (C) is 6 to 10 mol%, and is contained in the carboxylic acid unit (B) and the carboxylic acid.
- a "unit” means "a constituent unit of origin", for example, a carboxylic acid ester unit means a constituent unit derived from a carboxylic acid ester, and the carboxylic acid unit is a carboxylic acid.
- the carboxylic acid neutralizing substance unit indicates the carboxylic acid neutralizing substance-derived structural unit, and the ethylene unit indicates the ethylene-derived structural unit.
- (meth) acrylic acid means methacrylic acid or acrylic acid.
- the present inventor has focused on the monomer unit and the molecular weight of the ionomer resin, and found that 0.01 to 1.8 mol% of the carboxylic acid ester unit (A), the carboxylic acid unit (B), and the carboxylic.
- a specific ionomer resin containing an acid neutralizer unit (C) and an ethylene unit (D) and having a total content of units (A) to (C) of 6 to 10 mol% has a number average molecular weight of 8,000.
- the ionomer resin is contained.
- the self-supporting property in a high temperature environment means that when a resin sheet is used as an interlayer film for laminated glass for laminated glass, even if the glass is in a broken state in a high temperature environment, the broken glass is used. It means the property that it does not easily penetrate the resin sheet (interlayer film for laminated glass) or the property that the resin sheet does not drip easily.
- the property that the glass and the resin sheet easily adhere to each other means the property that the glass and the resin sheet easily adhere to each other
- the coloring property means the property that the glass sheet easily colors
- the transparency of the resin sheet means the transparency of the resin sheet itself and the transparency of the resin sheet itself. / Or, it means the transparency of the laminated glass formed by using the resin sheet as an interlayer film.
- the relaxed elastic modulus after a long period of time may be abbreviated as "long-term relaxed elastic modulus”.
- the resin sheet of the present invention can achieve both excellent low-temperature adhesiveness and excellent strength after a long period of time because it contains 2.6% by mass or more of a low molecular weight component at the time of producing laminated glass.
- the molten ionomer resin can follow the unevenness of the interface between the glass and the resin sheet (intermediate film), so that the adhesiveness can be effectively improved and the number average molecular weight of the ionomer resin is 8,000 to 14. It is presumed that since the amount is adjusted to 000 g / mol and the amount of the low molecular weight component is suppressed to 4.0% by mass or less, the decrease in the relaxed elastic coefficient during long-term use can be effectively suppressed.
- the ionomer resin of the present invention has a number average molecular weight (Mn) when the carboxylic acid unit (B) and the carboxylic acid neutralizer unit (C) are converted into methyl carboxylate units and the molecular weight in terms of polyethylene is measured by GPC. Is 8,000 to 14,000 g / mol, and the proportion of low molecular weight components having a molecular weight of 2,500 or less obtained from the integrated molecular weight distribution curve is 2.6 to 4.0% by mass. ..
- the number average molecular weight when the carboxylic acid unit (B) and the carboxylic acid neutralizer unit (C) are converted into the methyl carboxylate unit and the molecular weight in terms of polyethylene is measured by GPC is simply "number average”. It may be referred to as “molecular weight” or “Mn”, and a low molecular weight component having a molecular weight of 2,500 g / mol or less obtained from an integrated molecular weight distribution curve may be simply referred to as a "low molecular weight component".
- the obtained resin sheet tends not to have sufficient strength after a long period of time, and the number average molecular weight exceeds 14,000 g / mol. And, the molding processability of the ionomer resin tends to be inferior. Further, when the ratio of the low molecular weight component of the ionomer resin is less than 2.6% by mass, the obtained resin sheet tends not to have sufficient low-temperature adhesiveness, and the ratio of the low molecular weight component is 4.0% by mass. If it exceeds%, sufficient strength of the obtained resin sheet after a long period of time tends not to be obtained.
- the ionomer resin of the present invention has a number average molecular weight of 8,000 g / mol or more, preferably 8,500 g / mol or more, more preferably 9,000 g / mol or more, still more preferably 9,500 g / mol or more, and 14 It is 000 g / mol or less, preferably 13,000 g / mol or less, and more preferably 13,000 g / mol or less.
- the number average molecular weight is equal to or more than the above lower limit, it is easy to suppress a decrease in the long-term relaxation elastic modulus of the obtained resin sheet, so that it is easy to improve the strength after a long period of time, and the number average molecular weight is equal to or less than the above upper limit. Then, it is easy to improve the molding processability of the ionomer resin.
- the ionomer resin of the present invention has a low molecular weight component content of 2.6% by mass or more, preferably 2.7% by mass or more, more preferably 2.8% by mass or more, still more preferably 3.0% by mass or more, and further. It is more preferably 3.2% by mass or more, 4.0% by mass or less, and preferably 3.9% by mass or less.
- the ratio of the low molecular weight component is not more than the above lower limit, the low temperature adhesiveness of the obtained resin sheet is likely to be enhanced, and when the ratio of the low molecular weight component is not more than the above upper limit, the obtained resin sheet has long-term relaxation elastic modulus. Since it is easy to suppress the decrease in the rate, it is easy to improve the strength after a long period of time.
- the polyethylene-equivalent number average molecular weight and the proportion of low molecular weight components of the ionomer resin can be calculated as follows. First, the carboxylic acid unit (B) and the carboxylic acid neutralized product unit (C) of the ionomer resin are converted into the methyl carboxylate unit, and gel permeation chromatography (sometimes referred to as GPC) is performed on the converted ionomer resin. Use to measure the chromatogram. Next, a polyethylene-equivalent Mn is obtained from a calibration curve prepared using a polystyrene standard polymer by a Q factor.
- GPC gel permeation chromatography
- the ratio of the low molecular weight component having a molecular weight of 2,500 g / mol or less can be calculated from the integrated molecular weight distribution calculated using the calibration curve.
- Q Falter refer to "Size Exclusion Chromatography: High Performance Liquid Chromatography of Polymers” (1991, by Sadao Mori, Kyoritsu Shuppan Co., Ltd.).
- polystyrene 41.3 and polyethylene 17.7 are used as Q factors.
- the polyethylene-equivalent number average molecular weight and the ratio of the low molecular weight components of the ionomer resin can be calculated, for example, by the method described in Examples.
- the ionomer resin of the present invention may be composed of one type of ionomer resin or may be composed of two or more types of ionomer resin. When composed of two or more types of ionomer resins, each ionomer resin may have different constituent units and their proportions, or may have different molecular weights from each other.
- the ratio of Mn and low molecular weight components of the ionomer resin is the ratio of Mn and low molecular weight components of the ethylene-carboxylic acid ester copolymer (X) when the ethylene-carboxylic acid ester copolymer (X) is used as a raw material. Can be adjusted by changing as appropriate.
- ionomer resins when two or more kinds of ionomer resins are used, for example, even if ionomer resins having different Mns and / or different proportions of low molecular weight components are combined and adjusted to the desired proportions of Mn and low molecular weight components. good.
- the ionomer resin of the present invention contains a carboxylic acid ester unit (A), a carboxylic acid unit (B), a carboxylic acid neutralizer unit (C) and an ethylene unit (D).
- carboxylic acid ester unit (A) examples include unsaturated carboxylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and n (meth) acrylate.
- (meth) acrylic acid ester from the viewpoint of transparency of the obtained resin sheet, independence in a high temperature environment, strength after a long period of time, easy to improve low temperature adhesiveness, and easy to reduce colorability.
- methyl (meth) acrylate is particularly preferred.
- the methacrylic acid ester and the acrylic acid ester the methacrylic acid ester is preferable because it has excellent heat-decomposability and low coloring property.
- the carboxylic acid ester unit (A) can be used alone or in combination of two or more.
- the ionomer resin of the present invention has a carboxylic acid ester unit (A) content of 0.01 to 1.8 mol% based on all the monomer units constituting the ionomer resin.
- the content of the carboxylic acid ester unit (A) in the ionomer resin of the present invention is 0.01 mol% or more, preferably 0.03 mol% or more, based on all the monomer units constituting the ionomer resin. , More preferably 0.05 mol% or more, still more preferably 0.08 mol% or more, 1.8 mol% or less, preferably 1.5 mol% or less, more preferably 1.0 mol% or less, and further. It is preferably 0.9 mol% or less, still more preferably 0.8 mol% or less, and particularly preferably 0.6 mol% or less.
- the content of the carboxylic acid ester unit (A) is at least the above lower limit, the transparency of the obtained resin sheet can be easily increased, and when the content of the carboxylic acid ester unit (A) is at least the above upper limit, it is obtained. It is easy to increase the independence of the resin sheet to be obtained in a high temperature environment and the strength after a long period of time.
- carboxylic acid unit (B) examples of the monomer constituting the carboxylic acid unit (B) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, monomethyl maleate, and monoethyl maleate. Can be mentioned.
- acrylic acid, methacrylic acid from the viewpoints of transparency of the obtained resin sheet, independence in a high temperature environment, strength after a long period of time, easy to improve low temperature adhesiveness, and easy to reduce colorability, Monomethyl maleate and monoethyl maleate are preferable, acrylic acid and methacrylic acid are more preferable, and methacrylic acid is even more preferable.
- the carboxylic acid unit (B) can be used alone or in combination of two or more.
- the content of the carboxylic acid unit (B) in the ionomer resin of the present invention is preferably 1.0 mol% or more, more preferably 3.0 mol, based on all the monomer units constituting the ionomer resin. % Or more, more preferably 4.5 mol% or more, even more preferably 5.0 mol% or more, particularly preferably 5.5 mol% or more, particularly more preferably 5.8 mol% or more, preferably 10 It is 0.0 mol% or less, more preferably 9.0 mol% or less, still more preferably 8.5 mol% or less, still more preferably 8.0 mol% or less, and particularly preferably 7.5 mol% or less.
- the content of the carboxylic acid unit (B) is at least the above lower limit, the transparency and low-temperature adhesiveness of the obtained resin sheet can be easily enhanced, and the content of the carboxylic acid unit (B) is at least the above upper limit. And, it is easy to improve the molding processability of ionomer resin.
- the monomer constituting the carboxylic acid neutralized product unit (C) is preferably a neutralized product of the monomer constituting the carboxylic acid unit (B).
- the carboxylic acid neutralized product is obtained by replacing the hydrogen ion of the carboxylic acid with a metal ion.
- the metal ion include monovalent metals such as lithium, sodium and potassium; and ions of polyvalent metals such as magnesium, calcium, zinc, aluminum and titanium. These metal ions can be used alone or in combination of two or more. For example, it may be a combination of one or more monovalent metal ions and one or more divalent metal ions.
- the carboxylic acid neutralized product unit (C) can be used alone or in combination of two or more.
- the content of the carboxylic acid neutralizing substance unit (C) in the ionomer resin of the present invention is preferably 0.1 mol% or more, more preferably 0, based on all the monomer units constituting the ionomer resin. .3 mol% or more, more preferably 0.65 mol% or more, even more preferably 1.0 mol% or more, particularly preferably 1.3 mol% or more, particularly more preferably 1.5 mol% or more, most preferably. Is 1.6 mol% or more, preferably 3.0 mol% or less, more preferably 2.7 mol% or less, still more preferably 2.6 mol% or less, still more preferably 2.5 mol% or less. be.
- the content of the carboxylic acid neutralized substance unit (C) is at least the above lower limit, the transparency of the obtained resin sheet, the independence in a high temperature environment, the strength after a long period of time can be easily increased, and the coloring property can be increased. Is easy to reduce.
- the content of the carboxylic acid neutralized substance unit (C) is not more than the above upper limit, the molding processability of the ionomer resin is likely to be improved.
- the total content of the carboxylic acid ester unit (A), the carboxylic acid unit (B), and the carboxylic acid neutralizer unit (C) is the total monomer unit constituting the ionomer resin.
- the standard is 6 to 10 mol%.
- the total content of the carboxylic acid ester unit (A), the carboxylic acid unit (B), and the carboxylic acid neutralizer unit (C) is the total monomer unit constituting the ionomer resin.
- it is 6.0 mol% or more, preferably 6.5 mol% or more, more preferably 7.0 mol% or more, still more preferably 7.5 mol% or more, preferably 10 mol% or less, and more.
- It is preferably 9.9 mol% or less, more preferably 9.5 mol% or less, and even more preferably 9.3 mol% or less.
- the total content of the units (A) to (C) is at least the above lower limit, it is easy to improve the transparency of the obtained resin sheet and the low-temperature adhesion to the glass, and the total of the units (A) to (C).
- the content is 10 mol% or less, the molding processability of the ionomer resin tends to increase, and the long-term relaxation elastic modulus of the obtained resin sheet does not easily decrease, so that the strength after a long period of time tends to increase.
- the content of acrylic acid units (total content of acrylic acid ester unit, acrylic acid unit and acrylic acid neutralizer unit) among the monomer units constituting the ionomer resin is meta.
- the content is larger than the content of acrylic acid units (total content of methacrylic acid ester unit, methacrylic acid unit and methacrylic acid neutralized product unit), carboxylic acid ester unit (A), carboxylic acid unit (B), It is preferable that the total content of the carboxylic acid neutralizing substance unit (C) is relatively large.
- the total content of the units (A) to (C) is preferably 7.0 mol% or more, more preferably 7.5 mol%.
- the above is more preferably 8.0 mol% or more, further preferably 8.5 mol% or more, preferably 9.9 mol% or less, more preferably 9.8 mol% or less, still more preferably 9.7. It may be less than or equal to mol%, and even more preferably less than or less than 9.6 mol%.
- the ionomer resin of the present invention contains an ethylene unit (D).
- the content of the ethylene unit (D) in the ionomer resin is preferably 90 mol% or more, more preferably 90.1 mol% or more, still more preferably 90.1 mol% or more, based on all the monomer units constituting the ionomer resin. 90.5 mol% or more, still more preferably 90.7 mol% or more, preferably 94 mol% or less, more preferably 93.5 mol% or less, still more preferably 93 mol% or less, still more preferably 92. It is less than 5.5 mol%.
- the content of ethylene unit (D) is at least the above lower limit, mechanical properties and moldability can be easily improved, and when the content of ethylene unit (D) is at least the above upper limit, the obtained resin sheet can be obtained. Transparency and low temperature adhesion to glass tend to increase.
- the ionomer resin of the present invention may contain other monomer units other than the carboxylic acid ester unit (A), the carboxylic acid unit (B), the carboxylic acid neutralizer unit (C) and the ethylene unit (D). good.
- examples of other monomer units include propylene, n-butene, isobutene, vinyl acetate, vinyl alcohol and the like.
- Other monomer units can be used alone or in combination of two or more.
- the ionomer resin contains other monomer units, the content thereof may be appropriately selected within a range that does not impair the effects of the present invention, and is preferably based on all the monomer units constituting the ionomer resin. It is 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less.
- the contents of the carboxylic acid ester unit (A), the carboxylic acid unit (B), the carboxylic acid neutralized substance unit (C) and the ethylene unit (D) in the ionomer resin of the present invention can be analyzed by the following procedure. It is possible. First, the constituent units in the ionomer resin can be identified by pyrolysis gas chromatography (pyrolysis GC-MS), and then their contents can be evaluated using nuclear magnetic resonance spectroscopy (NMR) and elemental analysis. .. It is also possible to combine IR and Raman analysis. Prior to these analyzes, it is preferable to remove components other than the ionomer resin by a reprecipitation method or a Soxhlet extraction method.
- NMR nuclear magnetic resonance spectroscopy
- the contents of the carboxylic acid ester unit (A), the carboxylic acid unit (B), the carboxylic acid neutralized product unit (C) and the ethylene unit (D) in the ionomer resin of the present invention are determined by, for example, the method described in Examples. Can be calculated.
- the content of each of the carboxylic acid ester unit (A), the carboxylic acid unit (B) and the carboxylic acid neutralizer unit (C) is the ethylene-carboxylic acid ester copolymer (X).
- the carboxylic acid ester in the ethylene-carboxylic acid ester copolymer (X) The unit can be adjusted by the degree of reaction in each reaction to convert the carboxylic acid unit (B) and the carboxylic acid neutralizer unit (C) by the saponification reaction and the demetallization reaction.
- the total content of the units (A) to (C) can be adjusted by the ratio of the ethylene unit and the carboxylic acid ester unit of the ethylene-carboxylic acid ester copolymer (X) used as a raw material.
- the melting point of the ionomer resin of the present invention is preferably 50 ° C. to 200 ° C., more preferably 60 ° C. to 180 ° C., and 80 ° C. to 150 ° C. from the viewpoint of easily enhancing transparency and processability. Is even more preferable.
- the melting point for example, referring to the method described in JIS K7121: 2012, using differential scanning calorimetry (DSC), the cooling rate is -10 ° C / min and the heating rate is 10 ° C / min. It can be obtained from the peak picktop temperature.
- the heat of fusion of the ionomer resin of the present invention is preferably 0 J / g to 25 J / g from the viewpoint of easily increasing transparency.
- the cooling rate is -10 ° C / min and the heating rate is 10 ° C / min. It can be calculated from the area of the melting peak of.
- the melt flow rate (MFR) of the ionomer resin of the present invention measured under the conditions of 190 ° C. and 2.16 kgf is preferably 0.1 g / 10 minutes or more, more preferably 0.3 g / g. 10 minutes or more, more preferably 0.5 g / 10 minutes or more, still more preferably 0.7 g / 10 minutes or more, particularly preferably 0.9 g / 10 minutes or more, preferably 50 g / 10 minutes or less, more preferably. Is 30 g / 10 minutes or less, more preferably 10 g / 10 minutes or less, still more preferably 5 g / 10 minutes or less.
- the MFR of the ionomer resin can be adjusted by the molecular weight and the content of the carboxylic acid ester unit (A), the carboxylic acid unit (B), the carboxylic acid neutralizer unit (C) and the ethylene unit (D).
- the MFR of the ionomer resin of the present invention can be measured, for example, by the method described in Examples.
- the degree of branching per 1000 carbon atoms of the ionomer resin of the present invention is not particularly limited, but is preferably 5 to 30, and more preferably 6 to 20.
- the analysis of the degree of branching per 1000 carbons can be performed by the DDMAS method using, for example, solid-state NMR.
- the method for producing the ionomer resin of the present invention is not particularly limited, but for example, a step (I) of saponifying a part of an ethylene-carboxylic acid ester copolymer (X) (sometimes simply referred to as a copolymer (X)). ; And a method including a step (II) of demetallizing at least a part of the saponified product obtained by the step (I) can be mentioned.
- step (I) the ethylene-carboxylic acid ester copolymer (X) is preferably saponified with a strong base to convert a part of the carboxylic acid ester unit into a carboxylic acid neutralized product unit, resulting in a saponified product.
- An ethylene-carboxylic acid ester-carboxylic acid neutralized product copolymer is obtained.
- the ethylene-carboxylic acid ester copolymer (X) can be obtained, for example, by copolymerizing ethylene and a carboxylic acid ester at high temperature and high humidity.
- a carboxylic acid ester used as a raw material for example, the unsaturated carboxylic acid ester described above can be used.
- methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Sep-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate are preferable, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate and the like.
- (Meta) acrylic acid ester is more preferable.
- the methacrylic acid ester is preferable from the viewpoint of excellent heat-resistant decomposition of the obtained resin and low coloring property.
- the carboxylic acid ester can be used alone or in combination of two or more.
- ethylene-carboxylic acid ester copolymer (X) examples include an ethylene-methyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-ethyl methacrylate copolymer.
- Polymer ethylene-n-propyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-isopropyl methacrylate copolymer, ethylene-isopropyl methacrylate copolymer, n-butyl ethylene-acrylate
- examples thereof include a copolymer, an ethylene-n-butyl methacrylate copolymer, a sec-butyl copolymer of ethylene-acrylate, a sec-butyl copolymer of ethylene-methacrylate, and the like.
- Commercially available copolymers may be used, or these copolymers may be synthesized with reference to US Patent Application Publication No. 2013/0274424, JP-A-2006-23359, or JP-A-2007-84743. You may.
- the method for producing an ionomer resin comprises steps (I) and (II), and the content of the carboxylic acid ester unit contained in the ethylene-carboxylic acid ester copolymer (X) is high. , 6 to 10 mol% is preferable based on all the monomer units constituting the ethylene-carboxylic acid ester copolymer.
- the content of the carboxylic acid ester unit is in the above range, it is easy to adjust the content of the carboxylic acid unit (B) and the carboxylic acid neutralized product unit (C) of the obtained ionomer resin to a suitable range.
- the content of the carboxylic acid ester unit in the ethylene-carboxylic acid ester copolymer (X) is preferably 6.0 mol% or more, more preferably 6.5 mol% or more, still more preferably 7.0 mol% or more. , Even more preferably 7.5 mol% or more, preferably 10 mol% or less, more preferably 9.9 mol% or less, still more preferably 9.5 mol% or less, still more preferably 9.3 mol% or less. It is as follows.
- the content of the carboxylic acid ester unit in the copolymer (X) is the total content of the carboxylic acid ester unit (A), the carboxylic acid unit (B) and the carboxylic acid neutralized product unit (C) in the obtained ionomer resin.
- the content of the carboxylic acid ester unit in the copolymer (X) is equal to or higher than the above lower limit in order to correspond to the amount, the transparency of the obtained resin sheet and the low-temperature adhesion to the glass can be easily improved, and also.
- the content of the carboxylic acid ester unit in the polymer (X) is 10 mol% or less, the molding processability of the ionomer resin tends to be improved.
- the melt flow rate (MFR) of the ethylene-carboxylic acid ester copolymer (X) measured at 190 ° C. and 2.16 kgf is preferably 80 g / 10 minutes or more, more preferably. 90 g / 10 minutes or more, more preferably 100 g / 10 minutes or more, still more preferably 150 g / 10 minutes or more, preferably 400 g / 10 minutes or less, more preferably 350 g / 10 minutes or less, still more preferably 330 g / 10. Less than a minute.
- the MFR of the ethylene-carboxylic acid ester copolymer (X) can be adjusted by the degree of polymerization of the copolymer and the content of the carboxylic acid ester unit.
- the MFR of the ethylene-carboxylic acid ester copolymer (X) can be measured, for example, by the method described in Examples.
- the polyethylene-equivalent number average molecular weight (Mn) of the ethylene-carboxylic acid ester copolymer (X) is preferably 8,000 g / mol or more, more preferably 8,500 g / mol or more. It is more preferably 9,000 g / mol or more, still more preferably 9,500 g / mol or more, preferably 14,000 g / mol or less, more preferably 13,500 g / mol or less, still more preferably 13,000 g / mol. It is as follows.
- the Mn of the ethylene-carboxylic acid ester copolymer (X) is in the above range, the number average molecular weight and the ratio of the low molecular weight components of the obtained ionomer resin can be easily adjusted in the above range. The low-temperature adhesiveness of the obtained resin sheet and the strength after a long period of time are likely to be improved.
- Mn molecular weight of these ethylene-carboxylic acid ester copolymers (X)
- a column three series of TSKgel GMH HR -H (20) HT
- a 1,2,4-trichlorobenzene solvent were used. Therefore, it can be measured in terms of polyethylene under the condition of a column temperature of 140 ° C.
- the polyethylene-equivalent molecular weight can be calculated from a calibration curve prepared using a polystyrene standard polymer using the Q-factor described above.
- the number average molecular weight and the ratio of the low molecular weight components of the copolymer (X) are determined by the polymerization conditions of the monomer, for example, the type and amount of the polymerization initiator and the chain transfer agent, the polymerization temperature, and the polymerization mode (CSPR or plug flow method). Etc.) can be adjusted.
- the degree of branching of the ethylene-carboxylic acid ester copolymer (X) per 1000 carbons is not particularly limited, but is preferably 5 to 30, more preferably 6 to 20.
- the degree of branching can be measured by dissolving an ethylene-carboxylic acid ester copolymer in deuterated orthodichlorobenzene and using an inverse gate decoupling method of 13 C-NMR. Further, the degree of branching can be adjusted by the polymerization temperature or the like when the copolymer (X) is polymerized.
- Examples of strong bases that can be preferably used in the saponification reaction in the step (I) include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, which are soluble and economical in the solvent used in the saponification reaction. From the viewpoint, sodium hydroxide and potassium hydroxide are preferable.
- the amount of the strong base added is, for example, preferably 100 to 300 mol parts, more preferably 120 to 250 mol parts, and further, with respect to 100 mol parts of the carboxylic acid ester unit of the ethylene-carboxylic acid ester copolymer (X). It is preferably 150 to 200 mol parts.
- step (I) it is preferable to use a solvent for the saponification reaction.
- the solvent used for the saponification reaction include ethers such as tetrahydrofuran and dioxane; halogen-containing solvents such as chloroform and dichlorobenzene; ketones having 6 or more carbon atoms such as methylbutylketone; hydrocarbon compounds and methanol, ethanol, 1 -Mixed solvent with alcohols such as propanol, 2-propanol and 1-butanol; aromatic compounds such as benzene, toluene, xylene and ethylbenzene; mixed solvents of aromatic compounds and alcohols and the like can be mentioned.
- a preferable solvent is a mixed solvent of a hydrocarbon compound and alcohols, a mixed solvent of an aromatic compound and alcohols, and a more preferable solvent is toluene or the like. It is a mixed solvent of an aromatic compound and an alcohol such as methanol.
- the ratio of the hydrocarbon compound or aromatic compound to the alcohols in the mixed solvent may be appropriately selected according to the type of each solvent used, and for example, the mass ratio of the hydrocarbon compound or the aromatic compound to the alcohols ( The hydrocarbon compound or aromatic compound / alcohols) may be 50/50 to 90/10.
- the temperature at which the saponification reaction is carried out is preferably 50 ° C. or higher, more preferably 60 ° C. from the viewpoint of its reactivity and the solubility of the ethylene-carboxylic acid ester copolymer (X). Above, it is more preferably 70 ° C. or higher, particularly preferably 80 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 120 ° C. or lower.
- the saponification reaction may be carried out in air or in an inert gas such as nitrogen gas or argon gas. Further, the saponification reaction may be carried out under normal pressure, pressure, or reduced pressure, and is preferably carried out under pressure.
- Step (II) is a step of demetallizing at least a part of the saponified product obtained by step (I), that is, all or part of the saponified product.
- step (II) when a part of the saponified product is demetallized (referred to as step (II-a)), the carboxylic acid in the ethylene-carboxylic acid ester-carboxylic acid neutralized product copolymer which is the saponified product.
- a part of the acid neutralized product unit is preferably demetallized with a strong acid and converted into a carboxylic acid unit, whereby the carboxylic acid ester unit (A), the carboxylic acid unit (B), and the carboxylic acid neutralized product unit ( An ionomer resin containing C) and an ethylene unit (D) can be obtained. Further, in the case of demetallizing the entire saponified product in the step (II) (referred to as step (II-b)), the ethylene-carboxylic acid ester-carboxylic acid neutralized product copolymer which is the saponified product is contained.
- All of the carboxylic acid neutralizer units are preferably demetallized with a strong acid to convert them to carboxylic acid units to give an ethylene-carboxylic acid ester-carboxylic acid copolymer and then in the resulting demetallized product.
- a metal ion By neutralizing a part of the carboxylic acid unit with a metal ion and converting it into a (meth) acrylic acid neutralized product unit, the carboxylic acid ester unit (A), the carboxylic acid unit (B), and the carboxylic acid neutralized product are converted.
- An ionomer resin containing a unit (C) and an ethylene unit (D) can be obtained.
- Step (II) is carried out by step (II-a) or step (II-b), but from the viewpoint of reducing the number of reactions and easily improving the production efficiency of ionomer resin, step (II-a) is used for ionomer. It is preferable to produce a resin.
- Examples of strong acids used in the demetallization reaction in step (II) include hydrochloric acid, nitric acid, sulfuric acid, toluenesulfonic acid and the like.
- inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid are preferable from the viewpoint of easy washing and removal of salts by-produced from the strong base used in the saponification reaction and the strong acid used in the demetallization reaction.
- the solvent used for the demetallization the same solvent as the solvent used for the saponification reaction can be selected.
- the amount of the strong acid added can be selected according to the amount of the strong base added in order to adjust the carboxylic acid neutralizing substance unit (C) to an arbitrary value.
- the temperature at which the demetallization is performed is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 40 ° C. or higher, from the viewpoint of easily reducing the viscosity of the reaction solution. From the viewpoint of easily suppressing the excessive progress of corrosion of the transition metal due to the demetallization reaction, the temperature is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 120 ° C. or lower.
- the demetallization may be carried out in air or in an inert gas such as nitrogen gas or argon gas, as in the saponification reaction. Further, the demetallization may be performed under normal pressure, pressure, or reduced pressure.
- Examples of the neutralizing agent used for neutralizing a part of the carboxylic acid unit and converting it into the carboxylic acid neutralizing substance unit in the step (II-b) include an ionic compound containing a metal ion.
- the metal ion include alkali metal ions such as lithium, potassium and sodium, alkaline earth metal ions such as magnesium and calcium, transition metal ions such as zinc, nickel, iron and titanium, and aluminum ions.
- examples of the neutralizing agent include sodium hydroxide, sodium acetate, sodium hydrogencarbonate and the like.
- a polymer such as an ionomer resin containing a sodium carboxylate unit can also be used as a neutralizing agent.
- the crude ionomer resin which is a reaction product in the obtained reaction solution is separated and purified from the reaction mixture. Therefore, the ionomer resin of the present invention can be obtained. Separation and purification may be carried out by a conventional method, for example, separation means such as filtration, washing, concentration, reprecipitation, recrystallization and silica gel columntography.
- a poor solvent is added to a solution of a crude ionomer resin to precipitate a granular resin, and then the precipitated granular resin is used as a cleaning solution from the viewpoint of easy cleaning and removal of by-produced salts. It is preferable to carry out by washing with.
- the method for producing the ionomer resin of the present invention may include steps other than steps (I) and steps (II).
- the present invention includes a resin composition containing the ionomer resin of the present invention.
- the content of the ionomer resin contained in the resin composition of the present invention easily enhances the transparency of the obtained resin sheet, its independence in a high temperature environment, the strength after a long period of time, and the low temperature adhesiveness, and also improves the coloring property. From the viewpoint of easy reduction, it is preferably 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, based on the mass of the resin composition. It is preferably 99.9% by mass or less.
- the resin composition of the present invention may contain additives, if necessary.
- the additive include an ultraviolet absorber, an antioxidant, an antioxidant, a heat deterioration inhibitor, a light stabilizer, an anti-sticking agent, a lubricant, a mold release agent, a polymer processing aid, an antistatic agent, and a flame retardant.
- examples thereof include dyes and pigments, organic dyes, matting agents, and phosphors.
- ultraviolet absorbers, antioxidants, antioxidants, thermal deterioration inhibitors, light stabilizers, anti-glue agents, lubricants, mold release agents, polymer processing aids, and organic dyes are preferable.
- Additives can be used alone or in combination of two or more.
- the content of the additive can be appropriately determined as long as the effect of the present invention is not impaired, and is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, still more preferably 2% by mass. % Or less, preferably 0.1% by mass or more.
- the ultraviolet absorber is a compound having the ability to absorb ultraviolet rays, and is said to have the function of mainly converting light energy into heat energy.
- Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines and the like. These may be one kind alone or a combination of two or more kinds.
- Benzotriazoles are preferable as UV absorbers because they have a high effect of suppressing deterioration of optical properties such as coloring due to UV exposure.
- Examples of preferred benzotriazoles include 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN329), 2-.
- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name: TINUVIN234), 2,2'-methylenebis [6- (2H-benzo Triazole-2-yl) -4-t-octylphenol] (manufactured by ADEKA Co., Ltd .; LA-31), 2- (5-octylthio-2H-benzotriazole-2-yl) -6-tert-butyl-4- Examples thereof include methylphenol. These may be one kind alone or a combination of two or more kinds.
- triazine UV absorbers examples include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA Co., Ltd .; LA-). F70) and its analogs, hydroxyphenyltriazine-based ultraviolet absorbers (manufactured by BASF; TINUVIN477 and TINUVIN460), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3. 5-Triazine and the like can be mentioned. These may be one kind alone or a combination of two or more kinds.
- antioxidants examples include hydroquinone, hydroquinone monomethyl ether, 2,5-di-t-butylphenol, 2,6-di (t-butyl) -4-methylphenol, mono (or di or tri) ( ⁇ ).
- -Polymer compounds such as phenol (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4 Bisphenol compounds such as'-thiobis (3-methyl-6-t-butylphenol); benzimidazole compounds such as 2-mercaptobenzimidazole and 2-mercaptomethylbenzimidazole; 6-ethoxy-1,2-dihydro-2 , 2,4-trimethylquinoline, reaction product of diphenylamine and acetone, amine-ketone compounds such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer; N-phenyl-1-naphth
- the antioxidant is effective in preventing oxidative deterioration of the resin by itself in the presence of oxygen.
- phosphorus-based antioxidants hindered phenol-based antioxidants, thioether-based antioxidants, and the like can be mentioned. These antioxidants may be used alone or in combination of two or more. Among these, phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable, and a combination of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable from the viewpoint of the effect of preventing deterioration of optical properties due to coloring. preferable.
- the amount of the phosphorus-based antioxidant used is preferably 1: 5 to 2 in terms of mass ratio. 1, more preferably 1: 2 to 1: 1.
- Examples of preferable phosphorus-based antioxidants include 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (manufactured by ADEKA Corporation; trade name: ADEKA STAB HP-10), Tris (2). , 4-di-t-butylphenyl) phosphite (manufactured by BASF; trade name: IRGAFOS168), 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8 , 10-Tetraoxa 3,9-diphosphaspiro [5.5] Undecane (manufactured by ADEKA Corporation; trade name: ADEKA STUB PEP-36) and the like. These may be one kind alone or a combination of two or more kinds.
- antioxidants examples include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (BASF; trade name IRGANOX1010), octadecyl. -3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by BASF; trade name IRGANOX1076) and the like can be mentioned. These may be one kind alone or a combination of two or more kinds.
- the heat deterioration inhibitor can prevent the heat deterioration of the resin by capturing the polymer radicals generated when exposed to high heat under a substantially oxygen-free state.
- a preferable heat deterioration inhibitor 2-t-butyl-6- (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenylacrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name) Sumilyzer GM), 2,4-di-t-amyl-6- (3', 5'-di-t-amyl-2'-hydroxy- ⁇ -methylbenzyl) phenylacrylate (manufactured by Sumitomo Chemical Co., Ltd .; product The name simulator GS) and the like can be mentioned. These may be one kind alone or a combination of two or more kinds.
- the light stabilizer is a compound that is said to have a function of capturing radicals mainly generated by oxidation by light.
- suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton. These may be one kind alone or a combination of two or more kinds.
- anti-sticking agents examples include fatty acid salts or esters, polyhydric alcohol esters, inorganic salts, inorganic oxides, and particulate resins.
- preferable anti-sticking agents include calcium stearate, calcium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, silicon dioxide (manufactured by Ebonic; trade name Aerosil), particulate acrylic resin and the like. These may be one kind alone or a combination of two or more kinds.
- lubricants include stearic acid, behenic acid, stearomic acid, methylene bisstearoamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, hydrogenated oil and the like. These may be one kind alone or a combination of two or more kinds.
- the release agent examples include higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride. These may be one kind alone or a combination of two or more kinds.
- polymer particles having a particle diameter of 0.05 to 0.5 ⁇ m which can be produced by an emulsion polymerization method, are usually used.
- the polymer particles may be single-layer particles made of a polymer having a single composition ratio and a single extreme viscosity, or may be multilayer particles made of two or more kinds of polymers having different composition ratios or extreme viscosities. good. These may be one kind alone or a combination of two or more kinds.
- particles having a two-layer structure having a polymer layer having a low ultimate viscosity in the inner layer and a polymer layer having a high ultimate viscosity of 5 dl / g or more in the outer layer are preferable.
- the ultimate viscosity of the polymer processing aid is preferably 3 to 6 dl / g. If the ultimate viscosity is too small, the effect of improving the moldability tends to be low, and if the ultimate viscosity is too large, the moldability of the copolymer tends to be deteriorated.
- the organic dye a compound having a function of converting ultraviolet rays into visible light is preferably used.
- the organic dye may be used alone or in combination of two or more.
- fluorescent materials include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent whitening agents, fluorescent bleaching agents, and the like. These may be one kind alone or a combination of two or more kinds.
- the resin composition of the present invention can be obtained by adding the additive during or after the production of the ionomer resin of the present invention.
- the additive may be added to the polymerization or polymer reaction system in producing the ionomer resin, may be added in the step of separating the ionomer resin, or may be added after the separation. Further, it may be added at the time of manufacturing a molded product such as a film.
- the ionomer resin of the present invention and the resin composition of the present invention may be in the form of pellets or the like in order to enhance convenience during storage, transportation, or molding.
- the ionomer resin and the resin composition are pelletized, they can be obtained, for example, by cutting the strands obtained by the melt extrusion method.
- the temperature of the ionomer resin or the resin composition at the time of melt extrusion in the case of pelleting by the melt extrusion method is preferably 150 ° C. or higher, more preferably 170 ° C. or higher from the viewpoint of easily stabilizing the discharge from the extruder. Further, the temperature is preferably 250 ° C. or lower, more preferably 230 ° C.
- the ionomer resin of the present invention and the resin composition of the present invention have high heat-decomposability, problems such as thermal decomposition of the ionomer resin to generate black foreign matter are unlikely to occur when pelletizing by the melt extrusion method. .. Further, since the ionomer resin of the present invention and the resin composition of the present invention have little odor, the health of the worker can be ensured.
- the present invention includes a resin sheet containing the ionomer resin of the present invention or the resin composition of the present invention. Since the resin sheet of the present invention contains the ionomer resin of the present invention or the resin composition of the present invention, it is excellent in transparency and independence in a high temperature environment, has low coloring property, and is bonded to glass at a lower temperature than before. However, it has sufficient adhesiveness to glass and can have high strength even after a long period of time. Therefore, it can be suitably used as an interlayer film for laminated glass.
- the resin sheet of the present invention has excellent low-temperature adhesiveness.
- the temperature at the time of manufacturing the laminated glass for example, the temperature in the pressure crimping step described later is set to a relatively low temperature (for example, about 130 ° C.) to prepare the laminated glass, and the maximum shear stress of the obtained laminated glass is obtained. Can be evaluated by measuring.
- the maximum shear stress of the laminated glass containing the resin sheet of the present invention as an interlayer film for laminated glass is preferably 25 MPa or more, more preferably 26 MPa or more, still more preferably 27 MPa or more, particularly preferably. Is 28 MPa or more.
- the upper limit of the maximum shear stress is usually 60 MPa or less, preferably 55 MPa or less, more preferably 50 MPa or less, still more preferably 45 MPa or less, and particularly preferably 40 MPa or less.
- the maximum shear stress can be measured by, for example, the method described in Examples.
- the resin sheet of the present invention has excellent strength even after a long period of time.
- the strength after a long period of time is the relaxed elastic modulus after a long period of time (long-term relaxed elastic modulus), for example, 2.6 ⁇ 106 seconds after creating a master curve at 50 ° C. (about 1 month later). It can be evaluated by the relaxed elastic modulus in.
- the relaxation elastic modulus after 2.6 ⁇ 106 seconds (about 1 month) when the master curve is created at 50 ° C. is preferably 0.25 MPa or more, more preferably 0. It is 27 MPa or more, more preferably 0.29 MPa or more, particularly preferably 0.32 MPa or more, and most preferably 0.35 MPa or more.
- the resin sheet and the laminated glass having the resin sheet as an interlayer film can exhibit excellent strength after a long period of time.
- the upper limit of the relaxed elastic modulus is usually 5.0 MPa or less, preferably 4.0 MPa or less, more preferably 3.0 MPa or less, still more preferably 2.0 MPa or less, from the viewpoint of handleability of the resin sheet.
- the relaxed elastic modulus is determined from the dynamic viscoelasticity measurement and the time-temperature conversion rule using a dynamic viscoelasticity measuring device after the resin sheet is allowed to stand in an atmosphere of 23 ° C. and 50% RH for 1 week or longer. It can be obtained from the obtained synthetic curve (referred to as a master curve) having a reference temperature of 50 ° C., for example, by the method described in Examples.
- the resin sheet of the present invention has excellent independence in a high temperature environment.
- the independence in a high temperature environment can be evaluated by the storage elastic modulus at 50 ° C.
- the storage elastic modulus of the resin sheet of the present invention at 50 ° C. is preferably 30 MPa or more, more preferably 35 MPa or more, still more preferably 40 MPa or more, still more preferably 45 MPa or more, particularly preferably. It is 50 MPa or more, more preferably 55 MPa or more.
- the storage elastic modulus at 50 ° C. is at least the above lower limit, the resin sheet can exhibit excellent independence in a high temperature environment (for example, about 50 ° C.).
- the storage elastic modulus at 50 ° C. can be measured by using a dynamic viscoelasticity measuring device, for example, by the method described in Examples.
- the resin sheet of the present invention has low colorability and is preferably colorless.
- the yellowness (YI) of the resin sheet of the present invention is preferably 2.0 or less, more preferably 1.8 or less, still more preferably 1.5 or less, still more preferably 1.3 or less, and particularly preferably 1.0 or less. It is as follows. When the yellowness (YI) is not more than the above upper limit, the resin sheet and the laminated glass having the resin sheet as an interlayer film can exhibit low coloring property.
- the lower limit of yellowness (YI) is 0 or more.
- the yellowness (YI) can be measured according to JIS K7373 based on the value measured according to JIS Z8722 using a color difference meter, and can be calculated, for example, by the method described in Examples.
- the resin sheet of the present invention is excellent in the transparency of the sheet itself in a flat surface state without melt fracture or embossing on the surface, and is also excellent in the transparency of the laminated glass formed by forming the resin sheet as an interlayer film.
- the transparency of the laminated glass having the resin sheet of the present invention as an interlayer film is, for example, haze (slow cooling haze) when the laminated glass is heated to 140 ° C. and then slowly cooled to 23 ° C. at a rate of 0.1 ° C./min. It can be evaluated by (referred to as).
- the slow cooling haze is a haze in a state in which the crystallization of the ionomer resin is promoted by the slow cooling.
- the slow cooling haze of the laminated glass having the resin sheet of the present invention as an interlayer film is preferably 5.0% or less, more preferably 4.5% or less, still more preferably 4.0% or less, still more preferably 3. It is 5% or less, particularly preferably 3.0% or less.
- a laminated glass having a resin sheet as an interlayer film is prepared, the laminated glass is heated to 140 ° C., and then slowly cooled from 140 ° C. to 23 ° C. at a rate of 0.1 ° C./min. Is determined by measuring with a haze meter in accordance with JIS K7136: 2000, for example, by the method described in Examples.
- the resin sheet of the present invention preferably has a low water content from the viewpoint of adhesiveness to glass.
- the water content is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.02% by mass or less, and particularly preferably 0. It is 01% by mass or less.
- the content of the ionomer resin contained in the resin sheet of the present invention determines the transparency of the obtained resin sheet, its independence in a high temperature environment, its strength after a long period of time, and its low temperature adhesiveness.
- the resin sheet is preferably 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, based on the mass of the resin sheet. It is by mass or more, preferably 100% by mass or less.
- the thickness of the resin sheet of the present invention is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more, still more preferably 0.4 mm or more. Particularly preferably 0.5 mm or more, particularly more preferably 0.6 mm or more, most preferably 0.7 mm or more, preferably 5 mm or less, more preferably 4 mm or less, still more preferably 3 mm or less, still more preferably 1. It is 5 mm or less, particularly preferably 1.2 mm or less, and particularly more preferably 1 mm or less.
- the thickness of the resin sheet is at least the above lower limit, it is easy to increase the low temperature adhesiveness of the resin sheet and the strength after a long period of time, and when the thickness of the resin sheet is at least the above upper limit, the transparency of the resin sheet is transparent. It is easy to improve the property and reduce the colorability.
- the thickness of the resin sheet can be measured using, for example, a contact type or non-contact type thickness gauge, and can be measured, for example, by the method described in Examples. When the resin sheet is a laminated body, the thickness of the resin sheet indicates the thickness of the layer (x).
- the resin sheet of the present invention may be composed of only a layer (referred to as a layer (x)) containing the ionomer resin or the resin composition, and is a laminate containing at least one layer (x). May be.
- the laminate is not particularly limited, but is a laminate including another layer in addition to the layer (x), for example, a two-layer body in which a layer (x) and another layer are laminated, or two layers (x). Examples thereof include a laminated body in which another layer is arranged between the two.
- the resin sheet may be rolled up in a roll shape or may be in a single-wafered state.
- Examples of the other layer include a layer containing a known resin.
- the resin include polyethylene terephthalate, polybutylene terephthalate, cyclic polyolefin, and polyphenylene sulfide among polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polytetrafluoroethylene, acrylic resin, polyamide, polyacetal, polycarbonate, and polyester.
- Polytetrafluoroethylene, polysulfone, polyether sulfone, polyarylate, liquid crystal polymer, polyimide, thermoplastic elastomer and the like can be used.
- other layers may also be used as a plasticizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiblocking agent, a pigment, a dye, and a heat-shielding material (for example, an inorganic heat-shielding material having an infrared absorbing ability). It may contain additives such as fine particles or organic heat-shielding materials) and functional inorganic compounds.
- the ionomer resin or the resin composition is kneaded, preferably uniformly melt-kneaded, and then an extrusion method, a calendar method, a compression molding method, a press method, a solution casting method, a melt casting method, and an inflation method. It can be obtained by forming the layer (x) by a known film-forming method such as.
- the layer (x) and another layer may be laminated by press molding or the like to form a laminated resin sheet, or the layer (x) and the other layer may be laminated by a coextrusion method. It may be molded into a laminated resin sheet.
- the ionomer resin or the resin composition may be kneaded, preferably the additive may be added during melt kneading.
- a method for producing a resin sheet using a compression molding method or an extrusion method is particularly preferably used.
- the resin temperature during compression molding or extrusion is preferably 150 ° C. or higher, more preferably 170 ° C. or higher, preferably 250 ° C. or lower, and more preferably 230 ° C. or lower.
- the resin temperature is not more than the above upper limit, it is easy to suppress the decomposition and deterioration of the resin.
- the resin temperature is equal to or higher than the above lower limit, the moldability of the resin is likely to be improved.
- the ionomer resin of the present invention it is possible to form a film without deteriorating the working environment at the time of film formation.
- the resin sheet of the present invention may have an uneven structure formed on the surface by a conventionally known method such as melt fracture or embossing.
- a conventionally known method such as melt fracture or embossing.
- melt fracture and the embossing conventionally known shapes can be adopted. It is preferable to form an uneven structure on the surface of the resin sheet of the present invention from the viewpoint of excellent foam removal property when the resin sheet and a base material such as glass are thermocompression bonded.
- the present invention includes a laminated glass having two glass plates and an interlayer film arranged between the two glass plates, wherein the interlayer film is the resin sheet of the present invention. Since the laminated glass of the present invention has the resin sheet of the present invention as an interlayer film, it is excellent in transparency and self-supporting in a high temperature environment, has low coloring property, and is a glass and a resin sheet at a temperature lower than the conventional one in the manufacturing process. It has sufficient adhesiveness even when laminated with an interlayer film), and can maintain high strength even after a long period of time.
- the glass plate laminated with the resin sheet of the present invention is, for example, an inorganic glass such as a float plate glass, a tempered glass, a polished plate glass, a template glass, a braided plate glass, and a heat ray absorbing plate glass, as well as conventionally known materials such as polymethyl methacrylate and polycarbonate.
- Organic glass, etc. can be used. These may be either colorless or colored. These may be used alone or in combination of two or more.
- the thickness of the glass is preferably 100 mm or less.
- the laminated glass formed by sandwiching the resin sheet of the present invention between two sheets of glass can be manufactured by a conventionally known method.
- a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, a method using a nip roll, and the like can be mentioned.
- a vacuum laminator device for example, under a reduced pressure of 1 ⁇ 10 -6 to 1 ⁇ 10 -1 MPa, a glass plate, a resin sheet (intermediate film), and optionally adhesiveness at 60 to 200 ° C, especially 80 to 160 ° C.
- a resin layer, an organic glass plate, or the like may be laminated.
- a method using a vacuum bag or a vacuum ring is described in, for example, European Patent No. 1235683, which is laminated at 100 to 160 ° C. under a pressure of about 2 ⁇ 10 ⁇ 2 to 3 ⁇ 10 ⁇ 2 MPa. May be good.
- a method of degassing with a roll at a temperature equal to or lower than the flow start temperature of the resin sheet (intermediate film) and then crimping at a temperature closer to the flow start temperature there is a method of heating to 30 to 70 ° C. with an infrared heater or the like, degassing with a roll, further heating to 50 to 120 ° C., and then crimping with a roll can be mentioned.
- the operating conditions of the autoclave process are appropriately selected depending on the thickness and configuration of the laminated glass, and the pressure is, for example, 0.5 to 1.5 MPa. Lower, it is preferable to treat at 100 to 160 ° C. for 0.5 to 3 hours.
- the heat crimping step may include a step of pre-bonding with the vacuum laminator or the like and a step of main-bonding with an autoclave or the like.
- the laminated glass of the present invention is formed of a resin sheet containing an ionomer resin containing 2.6% by mass or more of a low molecular weight component or a resin composition containing an ionomer resin, the heat-bonding step described above, for example, the present bonding. Even if the crimping temperature is relatively low (for example, even at about 130 ° C.), the adhesiveness between the glass and the resin sheet is excellent.
- the maximum shear stress that is an index of the low temperature adhesiveness of the laminated glass of the present invention is the same as the maximum shear stress of the laminated glass described in the section of [Resin Sheet].
- the laminated glass of the present invention contains an ionomer resin having a predetermined number average molecular weight and a low molecular weight component of 4.0% by mass or less, or a resin composition containing the ionomer resin, and has a long-term relaxation modulus. Since it is made of a resin sheet having a high rate, excellent strength can be maintained even after a long period of time (for example, about one month).
- the laminated glass of the present invention has excellent transparency, and in particular, the haze (slow cooling haze) when the laminated glass is heated to 140 ° C. and then slowly cooled to 23 ° C. at a rate of 0.1 ° C./min is low.
- the slow cooling haze is a haze in a state in which the crystallization of the ionomer resin is promoted by the slow cooling.
- the slow-cooling haze of the laminated glass of the present invention is preferably 5.0% or less, more preferably 4.5% or less, still more preferably 4.0% or less, still more preferably 3.5% or less, and particularly preferably. It is 3.0% or less. The smaller the haze, the higher the transparency of the ionomer resin.
- the lower limit is not particularly limited, and may be, for example, 0.01% or more.
- Slow cooling haze measures the haze after heating the laminated glass to 140 ° C and then slowly cooling it from 140 ° C to 23 ° C at a rate of 0.1 ° C / min using a haze meter in accordance with JIS K7136: 2000. It can be measured by, for example, the method described in Examples.
- the laminated glass of the present invention is less colored and is preferably colorless.
- the yellowness (YI) of the laminated glass of the present invention can be selected from the same range as the yellowness (YI) of the resin sheet described in the section of [Resin Sheet].
- the resin sheet containing the ionomer resin of the present invention and the resin composition containing the ionomer resin of the present invention is useful as an interlayer film for laminated glass.
- the laminated glass interlayer film is particularly preferable as a laminated glass interlayer film for structural materials because it is excellent in adhesiveness, transparency, self-supporting property, and strength to a substrate such as glass.
- it is not limited to the interlayer film of laminated glass for structural materials, but also for automobile front glass, automobile side glass, automobile sun roof, automobile rear glass, head-up display glass, and other moving objects such as automobiles, outer walls and roofs.
- interlayer film for laminated glass in various applications such as laminates, panels, doors, windows, walls, roofs, sun roofs, sound insulation walls, display windows, balconies, handrail walls and other buildings, partition glass members for chambers, solar cells, etc. Suitable, but not limited to these uses.
- the ionomer resins obtained in Examples and Comparative Examples were each dissolved in a mixed solvent of dehydrated toluene / dehydrated acetic acid (75/25% by mass), reacted at 100 ° C. for 2 hours, and then acetone / water (80/20).
- the carboxylic acid neutralizer unit (C) was converted to the carboxylic acid unit (B) by reprecipitation in a mixed solvent of (% by mass).
- the obtained resin was sufficiently washed with water, dried, and the following (1) to (3) were performed on the dried resin.
- the components of the monomer units constituting the resin were analyzed by thermal decomposition GC-MS.
- the acid value of the resin was measured according to JIS K0070-1992.
- the ethylene unit (D) / carboxylic acid ester unit (A) / (carboxylic acid unit (B) and carboxylic acid neutralized product unit (C)) Total) ratio was calculated. Further, from the information in (4) above, the ratio of ethylene unit (D) / carboxylic acid ester unit (A) / carboxylic acid unit (B) / carboxylic acid neutralized product unit (C) was calculated.
- melt flow rate (MFR) According to JIS K7210, the melt flow rates of the ethylene-carboxylic acid ester copolymer (X) used in Examples and Comparative Examples and the ionomer resin obtained in Examples and Comparative Examples were measured. Specifically, each copolymer or each resin is melted in a cylinder and extruded from a die having a specified diameter (2.095 mm) installed at the bottom of the cylinder under a load condition of 190 ° C. and 2.16 kg. The amount of resin extruded per minute (g / min) was measured and converted into the amount of resin extruded per 10 minutes (g / 10 minutes) to determine the melt flow rate.
- MFR melt flow rate
- the molecular weights of the ionomer resins obtained in Examples and Comparative Examples were measured as follows.
- the ionomer resins obtained in Examples and Comparative Examples were dissolved by heating in a mixed solvent of acetic acid / toluene, and the carboxylic acid neutralized product unit was converted into a carboxylic acid unit. Further, the carboxylic acid unit was esterified to methyl carboxylate with trimethylsilyldiazomethane.
- the ionomer resin obtained by converting the carboxylic acid neutralizing substance unit and the carboxylic acid unit into the methyl carboxylate unit is heat-dissolved in 1,2,4-trichlorobenzene to which 0.1% of BHT (dibutylhydroxytoluene) is added. Then, it was heated and filtered with a 0.5 ⁇ m sintered filter.
- BHT dibutylhydroxytoluene
- a chromatogram was measured by gel permeation chromatography (GPC) under the following conditions, and a polyethylene-equivalent number average molecular weight (Mn) and a molecular weight distribution were calculated.
- the polyethylene-equivalent molecular weight is a value obtained by converting the standard polystyrene-equivalent molecular weight into the polyethylene-equivalent molecular weight using Q Falter.
- the baseline is the point where the slope of the peak on the high molecular weight side of the GPC chart changes from zero to positive when viewed from the earliest retention time, and the slope of the peak on the low molecular weight side is negative when viewed from the earlier retention time. The line connecting the points that change from to zero.
- the ratio of low molecular weight components having a molecular weight of 2500 or less was calculated from the integrated molecular weight distribution calculated using the calibration curve.
- GPC device HLC-8320 manufactured by Tosoh Corporation Detector: Differential refractive index detector Column: One of TSKgel guardcolumnH HR (30) (7.5 mm ID x 7.5 cm) manufactured by Tosoh Corporation and TSKgel GMH HR -H (20) HT (7.8 mmT) The one in which three of (D. ⁇ 30 cm) were connected in series was used. Eluent: 1,2,4-trichlorobenzene + BHT (0.05%) Eluent flow rate: 1.0 ml / min Sample injection volume: 0.3 ml Column temperature: 140 ° C Calibration curve: Created using data of 10 standard polystyrene points Q factor: Polystyrene 41.3, polyethylene 17.7 were used.
- the case where the long-term relaxation elastic modulus was 0.25 MPa or more was evaluated as "A”
- the case where the long-term relaxation elastic modulus was less than 0.25 MPa was evaluated as "B”.
- the tensile measurement is performed under the conditions of a temperature of 50 to 100 ° C. and a frequency of 0.1, 0.5, 1, 5, 10, 50, 100 Hz according to a method based on JIS K 0129: 2005. From the obtained measurement results of the storage elastic modulus, a master curve was created with the reference temperature as 50 ° C.
- the obtained test sample was evaluated by the compression shear strength test described in International Publication No. 1999/058334.
- the maximum shear stress when the laminated glass was peeled off was used as an index of low-temperature adhesion to the glass. The higher the maximum shear stress, the higher the low temperature adhesion to the glass. In the evaluation of the low temperature adhesiveness with the glass, the case where the maximum shear stress was 25 MPa or more was evaluated as "A", and the case where the maximum shear stress was less than 25 MPa was evaluated as "B".
- the haze of the laminated glass after the slow cooling operation was measured using a haze meter HZ-1 (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7136: 2000.
- "A" is when the measured haze is 5.0% or less
- "B” is when it is more than 5.0% and 10% or less
- “C” is when it is more than 10%. It was evaluated as.
- EMMA Polymer of ethylene and methyl methacrylate
- EEA Polymer of ethylene and ethyl acrylate
- EMA Polymer modification of ethylene and methyl acrylate: Based on all monomer units constituting the resin Content of (meth) acrylic acid ester unit
- Example 1 (Ionomer resin) 100 parts by mass of EMMA2 in Table 1 was introduced into the reaction vessel, 233 parts by mass of toluene was added thereto, and the mixture was stirred at 60 ° C. under a pressure of 0.02 MPa to dissolve EMMA2. To the obtained solution, 96 parts by mass of a methanol solution of sodium hydroxide (20% by mass) was added, and the mixture was stirred at 100 ° C. for 4 hours to saponify EMMA2, and a part of the methyl methacrylate unit was converted into sodium methacrylate unit. Converted.
- the obtained granular ionomer resin was vacuum-dried for 8 hours or more, and then melt-kneaded at 210 ° C. at a rotation speed of 90 rpm for 3 minutes using a batch type melt-kneader to obtain an ionomer resin.
- Example 2 Using EMMA3 shown in Table 1, an ionomer resin and a resin sheet were obtained in the same manner as in Example 1 except that 100 parts by mass of a methanol solution of sodium hydroxide and 83 parts by mass of hydrochloric acid (20% by mass) were added. rice field.
- Example 3 Same as Example 1 except that 100 parts by mass of a methanol solution of sodium hydroxide and 83 parts by mass of hydrochloric acid (20% by mass) were added using EMMA3 shown in Table 1 and the saponification reaction time was changed to 2 hours. Then, an ionomer resin and a resin sheet were obtained.
- Example 4 Same as Example 1 except that 70 parts by mass of EMMA4 and 30 parts by mass of EMMA5 in Table 1 were used, 104 parts by mass of a methanol solution of sodium hydroxide and 83 parts by mass of hydrochloric acid (20% by mass) were added. Then, an ionomer resin and a resin sheet were obtained.
- Example 5 The ionomer resin and the resin sheet were obtained in the same manner as in Example 1 except that 78 parts by mass of hydrochloric acid (20% by mass) was added using the EEA shown in Table 1.
- Example 6 Using the EMA shown in Table 1, an ionomer resin and a resin sheet were obtained in the same manner as in Example 1 except that 111 parts by mass of a methanol solution of sodium hydroxide and 91 parts by mass of hydrochloric acid (20% by mass) were added. rice field.
- Example 1 Using EMMA1 shown in Table 1, an ionomer resin and a resin sheet were obtained in the same manner as in Example 1 except that 72 parts by mass of a methanol solution of sodium hydroxide and 58 parts by mass of hydrochloric acid (20% by mass) were added. rice field.
- Example 3 Using EMMA4 shown in Table 1, an ionomer resin and a resin sheet were obtained in the same manner as in Example 1 except that 100 parts by mass of a methanol solution of sodium hydroxide and 83 parts by mass of hydrochloric acid (20% by mass) were added. rice field.
- Example 4 Same as Example 1 except that 100 parts by mass of a methanol solution of sodium hydroxide and 83 parts by mass of hydrochloric acid (20% by mass) were added using EMMA3 shown in Table 1 to change the saponification reaction temperature to 80 ° C. Then, an ionomer resin and a resin sheet were obtained.
- the resin sheets obtained in Examples and Comparative Examples are self-sustaining in a high temperature environment, strength after a long period of time, colorability and adhesiveness to glass, and transparency of laminated glass during slow cooling.
- the results were shown in Table 2.
- Table 2 the values obtained by measuring the storage elastic modulus at 50 ° C., the long-term relaxation elastic modulus, the yellowness (YI), the maximum shear stress, and the slow cooling haze are shown in parentheses.
- the ionomer resins used in Examples and Comparative Examples were analyzed according to the above method, and the results are also shown in Table 2.
- the content of the carboxylic acid ester unit (A) [(meth) acrylic acid ester unit] is the ester (A)
- the content of the carboxylic acid unit (B) [(meth) acrylic acid unit] is the acid (B).
- carboxylic acid ester unit (A), carboxylic acid unit (B) and
- the total content of the carboxylic acid unit (C) is expressed as (A) + (B) + (C), and each content is based on all the monomer units constituting the ionomer resin.
- the resin sheets made of ionomer resins obtained in Examples 1 to 6 are good in all evaluations of independence in a high temperature environment, strength after a long period of time, low temperature adhesion to glass, transparency, and colorability. It was confirmed that the evaluation was "A". On the other hand, it was confirmed that the resin sheet made of the ionomer resin obtained in Comparative Examples 1 to 7 had a poor evaluation "B" in at least one of them. Therefore, the ionomer resin of the present invention has excellent transparency, self-supporting property in a high temperature environment, low coloring property, and has sufficient adhesiveness to glass even when bonded to glass at a lower temperature than before. It is possible to form a resin sheet that can maintain high strength even after a long period of time.
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Abstract
Description
該アイオノマー樹脂を構成する全単量体単位を基準にして、カルボン酸エステル単位(A)の含有量が0.01~1.8モル%であり、かつカルボン酸エステル単位(A)、カルボン酸単位(B)、及びカルボン酸中和物単位(C)の合計含有量が6~10モル%であり、
カルボン酸単位(B)及びカルボン酸中和物単位(C)をカルボン酸メチル単位に変換して、GPCによりポリエチレン換算の分子量を測定した際に、積分分子量分布曲線から得られる分子量2,500以下の低分子量成分の割合が、2.6~4.0質量%であり、数平均分子量が8,000~14,000g/モルである、アイオノマー樹脂。
[2]カルボン酸中和物単位(C)の含有量が0.1~3.0モル%である、[1]に記載のアイオノマー樹脂。
[3]カルボン酸単位(B)の含有量が1.0~10.0モル%である、[1]又は[2]に記載のアイオノマー樹脂。
[4]カルボン酸エステル単位(A)は、(メタ)アクリル酸エステル単位である、[1]~[3]のいずれかに記載のアイオノマー樹脂。
[5]エチレン-カルボン酸エステル共重合体(X)の一部をけん化する工程(I);及び工程(I)により得られたけん化物の少なくとも一部を脱金属化する工程(II)を含み、
前記エチレン-カルボン酸エステル共重合体(X)に含まれるカルボン酸エステル単位の含有量は、該エチレン-カルボン酸エステル共重合体を構成する全単量体単位を基準にして、6~10モル%である、[1]~[4]のいずれかに記載のアイオノマー樹脂の製造方法。
[6]樹脂組成物の質量に対して90質量%以上の[1]~[4]のいずれかに記載のアイオノマー樹脂を含む、樹脂組成物。
[7][1]~[4]のいずれかに記載のアイオノマー樹脂、又は[6]に記載の樹脂組成物を含んでなる、樹脂シート。
[8]50℃でマスターカーブを作成した際の2.6×106秒後における緩和弾性率が、0.25MPa以上である、[7]に記載の樹脂シート。
[9]2つのガラス板と、該2つのガラス板の間に配置された中間膜とを有する合わせガラスであって、該中間膜が、[7]又は[8]に記載の樹脂シートである、合わせガラス。
本発明のアイオノマー樹脂は、カルボン酸エステル単位(A)、カルボン酸単位(B)、カルボン酸中和物単位(C)及びエチレン単位(D)を含み、該アイオノマー樹脂を構成する全単量体単位を基準にして、カルボン酸エステル単位(A)の含有量が0.01~1.8モル%であり、かつカルボン酸エステル単位(A)、カルボン酸単位(B)、及びカルボン酸中和物単位(C)の合計含有量(以下、「単位(A)~(C)の合計含有量」ということがある)が6~10モル%であり、カルボン酸単位(B)及びカルボン酸中和物単位(C)をカルボン酸メチル単位に変換して、GPCによりポリエチレン換算の分子量を測定した際に、積分分子量分布曲線から得られる分子量2500以下の低分子量成分の割合が、2.6~4.0質量%であり、数平均分子量が8,000~14,000g/モルである。なお、本明細書において、「単位」とは、「由来の構成単位」を意味するものであり、例えばカルボン酸エステル単位とはカルボン酸エステル由来の構成単位を示し、カルボン酸単位とはカルボン酸由来の構成単位を示し、カルボン酸中和物単位とはカルボン酸中和物由来の構成単位を示し、エチレン単位とはエチレン由来の構成単位を示す。また、本明細書において、「(メタ)アクリル酸」とは、メタクリル酸又はアクリル酸を示す。
本発明の樹脂シートが、特に、優れた低温接着性と、長時間経過後の優れた強度とを両立できるのは、低分子量成分を2.6質量%以上含むことにより、合わせガラス作製時の加熱圧着工程において、溶融したアイオノマー樹脂がガラスと樹脂シート(中間膜)との界面の凹凸に追随し得ることで有効に接着性を向上できるとともに、アイオノマー樹脂の数平均分子量が8,000~14,000g/モルに調整され、かつ低分子量成分が4.0質量%以下の量に抑制されているため、長時間使用時の緩和弾性率の低下を有効に抑制できるためと推定される。
本発明のアイオノマー樹脂において、カルボン酸エステル単位(A)を構成する単量体としては、不飽和カルボン酸エステル、例えば(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸sec-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸アミル、(メタ)アクリル酸イソアミル、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸フェニル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸グリシジル、(メタ)アクリル酸アリル等の(メタ)アクリル酸エステル;イタコン酸ジメチル;マレイン酸ジメチル;マレイン酸ジエチルなどが挙げられる。これらの中でも、得られる樹脂シートの透明性及び高温環境下における自立性、長時間経過後の強度、及び低温接着性を高めやすく、また着色性を低減しやすい観点から、(メタ)アクリル酸エステルが好ましく、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸sec-ブチル、(メタ)アクリル酸t-ブチルがより好ましく、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチルがさらに好ましく、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチルがさらにより好ましく、(メタ)アクリル酸メチルが特に好ましい。メタクリル酸エステルとアクリル酸エステルでは、メタクリル酸エステルの方が、耐熱分解性に優れ、低着色性であるため好ましい。カルボン酸エステル単位(A)は単独又は2種以上組み合わせて使用できる。
本発明のアイオノマー樹脂において、カルボン酸単位(B)を構成する単量体としては、不飽和カルボン酸、例えばアクリル酸、メタクリル酸、イタコン酸、無水マレイン酸、マレイン酸モノメチル、マレイン酸モノエチル等が挙げられる。これらの中でも、得られる樹脂シートの透明性及び高温環境下における自立性、長時間経過後の強度、及び低温接着性を高めやすく、また着色性を低減しやすい観点から、アクリル酸、メタクリル酸、マレイン酸モノメチル、マレイン酸モノエチルが好ましく、アクリル酸、メタクリル酸がより好ましく、メタクリル酸がさらに好ましい。カルボン酸単位(B)は単独又は2種以上組み合わせて使用できる。
本発明のアイオノマー樹脂において、カルボン酸中和物単位(C)を構成する単量体としては、カルボン酸単位(B)を構成する単量体の中和物が好ましい。該カルボン酸中和物は、カルボン酸の水素イオンを金属イオンで置き換えたものである。金属イオンとしては、リチウム、ナトリウム、カリウム等の1価金属;マグネシウム、カルシウム、亜鉛、アルミニウム、チタン等の多価金属のイオンが挙げられる。これらの金属イオンは、単独又は2種以上併用することができる。例えば、1価金属イオンの1種以上と2価金属イオンの1種以上の組み合わせであってもよい。カルボン酸中和物単位(C)は単独又は2種以上組み合わせて使用できる。
本発明のアイオノマー樹脂はエチレン単位(D)を含む。アイオノマー樹脂中のエチレン単位(D)の含有量は、該アイオノマー樹脂を構成する全単量体単位を基準にして、好ましくは90モル%以上、より好ましくは90.1モル%以上、さらに好ましくは90.5モル%以上、さらにより好ましくは90.7モル%以上であり、好ましくは94モル%以下、より好ましくは93.5モル%以下、さらに好ましくは93モル%以下、さらにより好ましくは92.5モル%以下である。エチレン単位(D)の含有量が上記の下限以上であると、機械的特性及び成形加工性を高めやすく、またエチレン単位(D)の含有量が上記の上限以下であると、得られる樹脂シートの透明性及びガラスとの低温接着性が高まりやすい。
本発明のアイオノマー樹脂の製造方法は、特に限定されないが、例えばエチレン-カルボン酸エステル共重合体(X)(単に共重合体(X)ということがある)の一部をけん化する工程(I);及び工程(I)により得られたけん化物の少なくとも一部を脱金属化する工程(II)を含む方法が挙げられる。
工程(I)では、エチレン-カルボン酸エステル共重合体(X)を、好ましくは強塩基によってけん化することにより、カルボン酸エステル単位の一部をカルボン酸中和物単位に変換して、けん化物であるエチレン-カルボン酸エステル-カルボン酸中和物共重合体を得る。
これらのうち、けん化反応前後の樹脂の溶解性の観点から、好ましい溶媒は炭化水素化合物とアルコール類との混合溶媒、芳香族化合物とアルコール類との混合溶媒であり、より好ましい溶媒はトルエン等の芳香族化合物とメタノール等のアルコール類との混合溶媒である。前記混合溶媒における炭化水素化合物又は芳香族化合物とアルコール類との割合は、用いる各溶媒の種類に応じて適宜選択すればよく、例えば、炭化水素化合物又は芳香族化合物とアルコール類との質量割合(炭化水素化合物又は芳香族化合物/アルコール類)は、50/50~90/10であってよい。
工程(II)は、工程(I)により得られたけん化物の少なくとも一部、すなわち、けん化物の全部又は一部を脱金属化する工程である。工程(II)において、けん化物の一部を脱金属化する場合(工程(II-a)と称する)、該けん化物であるエチレン-カルボン酸エステル-カルボン酸中和物共重合体中のカルボン酸中和物単位の一部を、好ましくは強酸により脱金属化して、カルボン酸単位に変換することにより、カルボン酸エステル単位(A)、カルボン酸単位(B)、カルボン酸中和物単位(C)及びエチレン単位(D)を含むアイオノマー樹脂を得ることができる。また、工程(II)において、けん化物の全部を脱金属化する場合(工程(II-b)と称する)、該けん化物であるエチレン-カルボン酸エステル-カルボン酸中和物共重合体中のカルボン酸中和物単位の全部を、好ましくは強酸により脱金属してカルボン酸単位に変換し、エチレン-カルボン酸エステル-カルボン酸共重合体を得て、次いで、得られた脱金属化物中のカルボン酸単位の一部を金属イオンによって中和して、(メタ)アクリル酸中和物単位に変換することにより、カルボン酸エステル単位(A)、カルボン酸単位(B)、カルボン酸中和物単位(C)及びエチレン単位(D)を含むアイオノマー樹脂を得ることができる。
本発明は、本発明のアイオノマー樹脂を含む樹脂組成物を包含する。本発明の樹脂組成物に含まれるアイオノマー樹脂の含有量は、得られる樹脂シートの透明性及び高温環境下における自立性、長時間経過後の強度、及び低温接着性を高めやすく、また着色性を低減しやすい観点から、該樹脂組成物の質量に対して、好ましくは90質量%以上、より好ましくは93質量%以上、さらに好ましくは95質量%以上、さらにより好ましくは98質量%以上であり、好ましくは99.9質量%以下である。
本発明は、本発明のアイオノマー樹脂又は本発明の樹脂組成物を含んでなる樹脂シートを包含する。本発明の樹脂シートは、本発明のアイオノマー樹脂又は本発明の樹脂組成物を含むため、透明性及び高温環境下における自立性に優れ、着色性が低く、従来よりも低い温度でガラスと貼り合わせてもガラスとの十分な接着性を有し、かつ、長時間経過しても高い強度を有することができる。そのため、合わせガラス用中間膜として好適に使用できる。
本発明は、2つのガラス板と、該2つのガラス板の間に配置された中間膜とを有する合わせガラスであって、該中間膜が本発明の樹脂シートである合わせガラスを包含する。本発明の合わせガラスは、本発明の樹脂シートを中間膜として有するため、透明性、高温環境下における自立性に優れ、着色性が低く、製造工程において従来よりも低い温度でガラスと樹脂シート(中間膜)とを貼り合わせても十分な接着性を有し、かつ、長時間経過しても高い強度を維持可能である。
カルボン酸エステル単位(A)、カルボン酸単位(B)、カルボン酸中和物単位(C)の含有量の分析は以下のようにして行った。
(1)熱分解GC-MSにより、樹脂を構成する単量体単位の成分を分析した。
(2)JIS K0070-1992に準じて、樹脂の酸価を測定した。
(3)重水素化トルエンと重水素化メタノールとの混合溶媒を用いて、樹脂の1H-NMR(400MHz、日本電子(株)製)測定を行った。
(4)また、実施例及び比較例で得られたアイオノマー樹脂を、それぞれ、硝酸によるマイクロ波分解前処理に付した後、ICP発光分析(Thermo Fisher Scientific社製、「iCAP6500Duo」)によって、カルボン酸中和物単位(C)の金属イオンの種類と量を同定した。
上記(1)から、カルボン酸エステル単位(A)及びカルボン酸単位(B)の種類と構造を同定した。その情報を基に、上記(2)及び(3)の情報から、エチレン単位(D)/カルボン酸エステル単位(A)/(カルボン酸単位(B)とカルボン酸中和物単位(C)の合計)の比率を算出した。さらに上記(4)の情報からエチレン単位(D)/カルボン酸エステル単位(A)/カルボン酸単位(B)/カルボン酸中和物単位(C)の比率を算出した。
JIS K7210に準拠して、実施例及び比較例で使用したエチレン-カルボン酸エステル共重合体(X)、及び実施例及び比較例で得られたアイオノマー樹脂のメルトフローレートを測定した。具体的には、各共重合体又は各樹脂をシリンダ内で溶融し、190℃、2.16kg荷重条件の下で、シリンダ底部に設置された規定口径(2.095mm)のダイスから押し出し、1分間あたりに押し出される樹脂量(g/分)を測定し、10分あたりに押し出される樹脂量(g/10分)に換算しメルトフローレートを求めた。
実施例及び比較例で得られたアイオノマー樹脂の分子量は、以下のようにして測定した。
実施例及び比較例で得られたアイオノマー樹脂を酢酸/トルエンの混合溶媒に加熱溶解させ、カルボン酸中和物単位をカルボン酸単位に変換した。さらにカルボン酸単位を、トリメチルシリルジアゾメタンによりカルボン酸メチルにエステル化させた。このようにカルボン酸中和物単位及びカルボン酸単位をカルボン酸メチル単位に変換させたアイオノマー樹脂を、BHT(ジブチルヒドロキシトルエン)を0.1%添加した1,2,4-トリクロロベンゼンに加熱溶解させ、次いで0.5μmの焼結フィルターで加熱ろ過した。得られたアイオノマー樹脂について、ゲルパーミエーションクロマトグラフィー(GPC)により、下記の条件でクロマトグラムを測定し、ポリエチレン換算の数平均分子量(Mn)及び分子量分布を算出した。ポリエチレン換算の分子量は、標準ポリスチレン換算の分子量をQファルターを用いてポリエチレン換算の分子量に換算した値である。なお、ベースラインはGPCチャートの高分子量側のピークの傾きが保持時間の早い方から見てゼロからプラスに変化する点と、低分子量側のピークの傾きが保持時間の早い方から見てマイナスからゼロに変化する点を結んだ線とした。
また、検量線を用いて算出した積分分子量分布から、分子量2500以下の低分子量成分の割合を算出した。
GPC装置:東ソー株式会社製、HLC-8320
検出器:示差屈折率検出器
カラム:東ソー株式会社製のTSKgel guardcolumnHHR(30)(7.5mmI.D.×7.5cm)の1本とTSKgel GMHHR-H(20)HT(7.8mmT.D.×30cm)の3本を直列に繋いだものを用いた。
溶離剤:1,2,4-トリクロロベンゼン+BHT(0.05%)
溶離剤流量:1.0ml/分
試料注入量:0.3ml
カラム温度:140℃
検量線:標準ポリスチレン10点のデータを用いて作成
Qファクター:ポリスチレン 41.3、ポリエチレン17.7 を用いた
実施例及び比較例で得られた樹脂シートから縦40mm×横5mmの試験片を切り出し、(株)UBM製動的粘弾性測定装置を用いて、測定温度50℃、周波数1Hz、昇温速度3℃/分の条件で、貯蔵弾性率(E’)を測定し、その値を高温環境下における樹脂シートの自立性の指標とした。50℃の貯蔵弾性率が高いほど、高温環境下における樹脂シートの自立性が高いことを示す。高温環境下における自立性の評価において、上記貯蔵弾性率が30MPa以上の場合を「A」、30MPa未満の場合を「B」として評価した。
実施例及び比較例で得られた樹脂シートを23℃、50%RH雰囲気下で1週間以上静置した後に、縦40mm×横5mmの試験片を切り出し、(株)UBM製動的粘弾性測定装置を用いて、動的粘弾性測定と時間-温度換算則から得られる、基準温度50℃の合成曲線(マスターカーブ)から長時間緩和弾性率を求め、その値を長時間経過後の樹脂シートの強度の指標とした。長時間緩和弾性率が高いほど、長時間経過後の樹脂シートの強度が高いことを示す。長時間経過後の樹脂シートの強度の評価において、上記長時間緩和弾性率が0.25MPa以上の場合を「A」、0.25MPa未満の場合を「B」として評価した。
動的粘弾性測定は、JIS K 0129:2005に準拠した方法に従い、温度50~100℃、周波数0.1、0.5、1、5、10、50、100Hzの条件下で引張測定を行い、得られた貯蔵弾性率の測定結果から、温度時間換算則を用いて、基準温度を50℃としてマスターカーブを作成し、周波数4.0×10-7Hzにおける貯蔵弾性率(E’(t1))、及び周波数2.0×10-7Hzにおける損失弾性率(E’’(t2))を読み取り、ポアソン比を0.5に固定し、下記式(A)により、50℃、2.6×106秒後の緩和弾性率G(t)を求めた。
G(t)=E’(t1)/3-0.4×E’’(t2)/3・・・(A)
なお、これらの一連の計算は、(株)UBM製動的粘弾性測定装置に付帯の計算ソフト「RheoStation」((株)UBM)を用いて行った。
実施例及び比較例で得られた樹脂シートを厚さ2.7mmのフロートガラス2枚に挟み、真空ラミネーター(日清紡メカトロニクス(株)製 1522N)を使用し、100℃で真空ラミネーター内を1分減圧し、減圧度及び温度を保持したまま30kPaで5分プレスして、仮接着体を得た。得られた仮接着体をオートクレーブに投入し、130℃、1.2MPaで30分処理して、合わせガラスを得た。
次いで、得られた合わせガラスを25mm×25mmの大きさに切断して試験サンプルを得た。得られた試験サンプルを国際公開第1999/058334号公報に記載の圧縮せん断強度試験(Compression shear strength test)により評価した。合わせガラスが剥離した際の最大せん断応力を、ガラスとの低温接着性の指標とした。最大せん断応力が高いほど、ガラスとの低温接着性が高いことを示す。ガラスとの低温接着性の評価において、上記最大せん断応力が25MPa以上であった場合を「A」、25MPa未満であった場合を「B」として評価した。
実施例及び比較例で得られた樹脂シートを日本電色工業(株)製の測色色差計「ZE-2000」(商品名)を用い、JIS Z8722に準拠して測定した。得られた値を元にJIS K7373に準拠して算出した黄色度の値をイエロインデックス(YI)とした。YIが低いほど、樹脂シートの着色性が低いことを示す。着色性の評価において、測定されたYIが2.0以下の場合を「A」、2.0超の場合を「B」として評価した。
実施例及び比較例で得られた樹脂シートを厚さ2.7mmのフロートガラス(日本板硝子製)2枚に挟み、真空ラミネーター(日清紡メカトロニクス(株)製 1522N)を使用し、100℃で真空ラミネーター内を1分減圧し、減圧度及び温度を保持したまま30kPaで5分プレスして、仮接着体を得た。得られた仮接着体をオートクレーブに投入し、140℃、1.2MPaで30分処理して、合わせガラスを得た。
得られた合わせガラスを140℃まで加熱したのち、0.1℃/分の速度で23℃まで徐冷した。徐冷操作後の合わせガラスのヘイズをヘイズメーターHZ-1(スガ試験機(株)製)を用いて、JIS K7136:2000に準拠して測定した。徐冷ヘイズが低いほど、合わせガラスを徐冷した際の透明性が高いことを示す。徐冷時の透明性の評価において、測定されたヘイズが5.0%以下の場合を「A」、5.0%超10%以下の場合を「B」、10%超の場合を「C」として評価した。
実施例及び比較例で得られた樹脂シートの厚さは、デジタルマイクロゲージを用いて測定した。
実施例及び比較例において、アイオノマー樹脂の原料として用いた各エチレン-(メタ)アクリル酸エステル共重合体(X)のメタクリル酸メチル(MMA)変性量又はアクリル酸エチル(EA)変性量、及びMFRを表1に示す。これらエチレン-(メタ)アクリル酸エステル共重合体(X)は、US2013/0274424、特開2006-233059又は特開2007-84743に記載の高温高圧ラジカル重合法にて合成することができる。例えば、EMMAとして住友化学(株)製「アクリフト」(登録商標)、EEAとして日本ポリエチレン(株)製「レクスパール」(登録商標)を用いることができる。
EMMA:エチレンとメタクリル酸メチルとの共重合体
EEA:エチレンとアクリル酸エチルとの共重合体
EMA:エチレンとアクリル酸メチルとの共重合体
変性量:樹脂を構成する全単量体単位を基準とする(メタ)アクリル酸エステル単位の含有量
(アイオノマー樹脂)
反応槽に、表1中のEMMA2 100質量部を導入し、そこにトルエン233質量部を加えて、0.02MPa加圧下、60℃で撹拌し、EMMA2を溶解させた。得られた溶液に水酸化ナトリウムのメタノール溶液(20質量%)96質量部を添加し、100℃で4時間撹拌し、EMMA2をけん化して、メタクリル酸メチル単位の一部をメタクリル酸ナトリウム単位に変換した。次いで、この溶液を50℃まで冷却した後に、塩酸(20質量%)79質量部を反応液中に添加し、50℃で1時間撹拌して、メタクリル酸ナトリウム単位の一部をメタクリル酸に変換し、粗アイオノマー樹脂溶液を得た。
得られた粗アイオノマー樹脂溶液にトルエン/メタノール(75/25質量%)の混合溶媒を粗アイオノマー樹脂濃度が10質量%となるように添加して、該溶液を希釈した。次いで、得られた粗アイオノマー樹脂の希釈溶液を34℃に調整した後、前記希釈溶液に34℃のメタノールを粗アイオノマー樹脂溶液100質量部に対して430質量部添加して、粒状樹脂を析出させた。次いで、得られた粒状樹脂を濾取した後、濾取した粒状樹脂100質量部と水/メタノール(50/50質量%)の混合溶媒600質量部とを混合した。前記混合により得られたスラリーを40℃で1時間撹拌し、その後、粒状樹脂を室温にて濾取した。水/メタノールの混合溶媒による粒状樹脂の洗浄をさらに3回行い、洗浄された粒状アイオノマー樹脂を得た。得られた粒状アイオノマー樹脂を8時間以上真空乾燥した後、バッチ式溶融混練機を用いて210℃、回転数90rpm、3分間溶融混錬してアイオノマー樹脂を得た。
得られたアイオノマー樹脂の溶融混練物を210℃加熱下、50kgf/cm2の圧力により5分間圧縮成形し、厚さ0.8mmの樹脂シートを得た。
表1にあるEMMA3を用い、水酸化ナトリウムのメタノール溶液100質量部、及び塩酸(20質量%)83質量部を添加したこと以外は、実施例1と同様にして、アイオノマー樹脂及び樹脂シートを得た。
表1にあるEMMA3を用い、水酸化ナトリウムのメタノール溶液100質量部、及び塩酸(20質量%)83質量部を添加し、けん化反応時間を2時間に変えたこと以外は、実施例1と同様にして、アイオノマー樹脂及び樹脂シートを得た。
表1にあるEMMA4を70質量部及びEMMA5を30質量部用い、水酸化ナトリウムのメタノール溶液104質量部、及び塩酸(20質量%)83量部を添加したこと以外は、実施例1と同様にして、アイオノマー樹脂及び樹脂シートを得た。
表1にあるEEAを用い、塩酸(20質量%)78質量部を添加したこと以外は、実施例1と同様にして、アイオノマー樹脂及び樹脂シートを得た。
表1にあるEMAを用い、水酸化ナトリウムのメタノール溶液111質量部、及び塩酸(20質量%)91質量部を添加したこと以外は、実施例1と同様にして、アイオノマー樹脂及び樹脂シートを得た。
表1にあるEMMA1を用い、水酸化ナトリウムのメタノール溶液72質量部、及び塩酸(20質量%)58質量部を添加したこと以外は、実施例1と同様にして、アイオノマー樹脂及び樹脂シートを得た。
塩酸(20質量%)90質量部を添加したこと以外は、実施例1と同様にして、アイオノマー樹脂及び樹脂シートを得た。
表1にあるEMMA4を用い、水酸化ナトリウムのメタノール溶液100質量部、及び塩酸(20質量%)83質量部を添加したこと以外は、実施例1と同様にして、アイオノマー樹脂及び樹脂シートを得た。
表1にあるEMMA3を用い、水酸化ナトリウムのメタノール溶液100質量部、及び塩酸(20質量%)83質量部を添加し、けん化反応温度を80℃に変えたこと以外は、実施例1と同様にして、アイオノマー樹脂及び樹脂シートを得た。
表1にあるEMMA5を用い、水酸化ナトリウムのメタノール溶液112質量部、及び塩酸(20質量%)84質量部を添加したこと以外は、実施例1と同様にして、アイオノマー樹脂及び樹脂シートを得た。
米国特許第6518365号に記載の方法を参考に、エチレン及びメタアクリル酸を共重合してエチレン-(メタ)アクリル酸共重合体を得た後、該共重合体を水酸化ナトリウムにより部分中和することにより表2に記載の組成のアイオノマー樹脂(Ionomer1と表記することがある)を得た。得られたアイオノマー樹脂を用いて、実施例1と同様の方法により樹脂シートを得た。
〔比較例7〕
米国特許第6518365号に記載の方法を参考に、エチレン、メタアクリル酸及びアクリル酸t-ブチルを共重合してエチレン-(メタ)アクリル酸-アクリル酸t-ブチル共重合体を得た後、該共重合体を水酸化ナトリウムにより部分中和することにより、表2に記載の組成のアイオノマー樹脂(Ionomer2と表記することがある)を得た。得られたアイオノマー樹脂を用いて、実施例1と同様の方法により樹脂シートを得た。
また、上記方法に従って、実施例及び比較例で使用したアイオノマー樹脂を分析し、その結果も表2に示した。表2中、カルボン酸エステル単位(A)[(メタ)アクリル酸エステル単位]の含有量をエステル(A)、カルボン酸単位(B)[(メタ)アクリル酸単位]の含有量を酸(B)、カルボン酸中和物単位(C)[(メタ)アクリル酸中和物単位]の含有量を中和物(C)、及び、カルボン酸エステル単位(A)、カルボン酸単位(B)及びカルボン酸単位(C)の合計含有量を(A)+(B)+(C)と表記し、各含有量はアイオノマー樹脂を構成する全単量体単位を基準としたものである。
Claims (9)
- カルボン酸エステル単位(A)、カルボン酸単位(B)、カルボン酸中和物単位(C)及びエチレン単位(D)を含むアイオノマー樹脂であって、
該アイオノマー樹脂を構成する全単量体単位を基準にして、カルボン酸エステル単位(A)の含有量が0.01~1.8モル%であり、かつカルボン酸エステル単位(A)、カルボン酸単位(B)、及びカルボン酸中和物単位(C)の合計含有量が6~10モル%であり、
カルボン酸単位(B)及びカルボン酸中和物単位(C)をカルボン酸メチル単位に変換して、GPCによりポリエチレン換算の分子量を測定した際に、積分分子量分布曲線から得られる分子量2500g/モル以下の低分子量成分の割合が、2.6~4.0質量%であり、数平均分子量が8,000~14,000g/モルである、アイオノマー樹脂。 - カルボン酸中和物単位(C)の含有量が0.1~3.0モル%である、請求項1に記載のアイオノマー樹脂。
- カルボン酸単位(B)の含有量が1.0~10.0モル%である、請求項1又は2に記載のアイオノマー樹脂。
- カルボン酸エステル単位(A)は、(メタ)アクリル酸エステル単位である、請求項1~3のいずれかに記載のアイオノマー樹脂。
- エチレン-カルボン酸エステル共重合体(X)の一部をけん化する工程(I);及び工程(I)により得られたけん化物の少なくとも一部を脱金属化する工程(II)を含み、
前記エチレン-カルボン酸エステル共重合体(X)に含まれるカルボン酸エステル単位の含有量は、該エチレン-カルボン酸エステル共重合体を構成する全単量体単位を基準にして、6~10モル%である、請求項1~4のいずれかに記載のアイオノマー樹脂の製造方法。 - 樹脂組成物の質量に対して90質量%以上の請求項1~4のいずれかに記載のアイオノマー樹脂を含む、樹脂組成物。
- 請求項1~4のいずれかに記載のアイオノマー樹脂、又は請求項6に記載の樹脂組成物を含んでなる、樹脂シート。
- 50℃でマスターカーブを作成した際の2.6×106秒後における緩和弾性率が、0.25MPa以上である、請求項7に記載の樹脂シート。
- 2つのガラス板と、該2つのガラス板の間に配置された中間膜とを有する合わせガラスであって、該中間膜が、請求項7又は8に記載の樹脂シートである、合わせガラス。
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WO2022270540A1 (ja) * | 2021-06-23 | 2022-12-29 | 株式会社クラレ | アイオノマー樹脂組成物を含んでなる層を有する樹脂シートおよび合わせガラス |
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JP7124246B1 (ja) | 2022-08-23 |
EP4253428A1 (en) | 2023-10-04 |
KR20220163524A (ko) | 2022-12-09 |
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