JPWO2016060176A1 - Laminated glass and interlayer film for laminated glass - Google Patents
Laminated glass and interlayer film for laminated glass Download PDFInfo
- Publication number
- JPWO2016060176A1 JPWO2016060176A1 JP2016554111A JP2016554111A JPWO2016060176A1 JP WO2016060176 A1 JPWO2016060176 A1 JP WO2016060176A1 JP 2016554111 A JP2016554111 A JP 2016554111A JP 2016554111 A JP2016554111 A JP 2016554111A JP WO2016060176 A1 JPWO2016060176 A1 JP WO2016060176A1
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- copolymer
- carboxylic acid
- unsaturated carboxylic
- ester copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005340 laminated glass Substances 0.000 title claims abstract description 54
- 239000011229 interlayer Substances 0.000 title claims abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 170
- 239000005977 Ethylene Substances 0.000 claims abstract description 170
- 229920001577 copolymer Polymers 0.000 claims abstract description 129
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 52
- 238000002834 transmittance Methods 0.000 claims abstract description 39
- 239000011521 glass Substances 0.000 claims abstract description 31
- 229920000573 polyethylene Polymers 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims description 20
- 229920000554 ionomer Polymers 0.000 claims description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 claims description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- -1 2-ethylhexyl Chemical group 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000001023 inorganic pigment Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 7
- 150000001733 carboxylic acid esters Chemical class 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004611 light stabiliser Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 239000005341 toughened glass Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000006078 metal deactivator Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 201000004569 Blindness Diseases 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229920005603 alternating copolymer Polymers 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- UHFYYDAYJKGVAK-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) 2-chlorobenzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1Cl UHFYYDAYJKGVAK-UHFFFAOYSA-N 0.000 description 1
- GUGVZCUAAGOTEU-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) 2-phenoxyacetate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)COC1=CC=CC=C1 GUGVZCUAAGOTEU-UHFFFAOYSA-N 0.000 description 1
- OKRSVCKJPLEHEY-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) acetate Chemical compound CC(=O)OC1CC(C)(C)NC(C)(C)C1 OKRSVCKJPLEHEY-UHFFFAOYSA-N 0.000 description 1
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- JCAMPEQCOPAWBA-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) cyclohexanecarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1CCCCC1 JCAMPEQCOPAWBA-UHFFFAOYSA-N 0.000 description 1
- JMUOXOJMXILBTE-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 JMUOXOJMXILBTE-UHFFFAOYSA-N 0.000 description 1
- BUFCQVRLKYIQJP-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) prop-2-enoate Chemical compound CC1(C)CC(OC(=O)C=C)CC(C)(C)N1 BUFCQVRLKYIQJP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- VRWOEFJNMPHSTD-UHFFFAOYSA-N (2-octoxyphenyl)-phenylmethanone Chemical compound CCCCCCCCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 VRWOEFJNMPHSTD-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- VNFXPOAMRORRJJ-UHFFFAOYSA-N (4-octylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(CCCCCCCC)=CC=C1OC(=O)C1=CC=CC=C1O VNFXPOAMRORRJJ-UHFFFAOYSA-N 0.000 description 1
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-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
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
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- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- BGCSUUSPRCDKBQ-UHFFFAOYSA-N 2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OCOCC21COCOC2 BGCSUUSPRCDKBQ-UHFFFAOYSA-N 0.000 description 1
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- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
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- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- PHXLONCQBNATSL-UHFFFAOYSA-N 2-[[2-hydroxy-5-methyl-3-(1-methylcyclohexyl)phenyl]methyl]-4-methyl-6-(1-methylcyclohexyl)phenol Chemical compound OC=1C(C2(C)CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1(C)CCCCC1 PHXLONCQBNATSL-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
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- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CTIQLGJVGNGFEW-UHFFFAOYSA-L naphthol yellow S Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C([O-])=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CTIQLGJVGNGFEW-UHFFFAOYSA-L 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- WOTPFVNWMLFMFW-ISLYRVAYSA-N para red Chemical compound OC1=CC=C2C=CC=CC2=C1\N=N\C1=CC=C(N(=O)=O)C=C1 WOTPFVNWMLFMFW-ISLYRVAYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- NAQGCFBMSYBDFZ-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) propane-1,1,2,3-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(=O)OC1CC(C)(C)NC(C)(C)C1 NAQGCFBMSYBDFZ-UHFFFAOYSA-N 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- OIRRCMCATRAYJG-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) 1H-triazine-2,4,6-tricarboxylate Chemical compound CC1(NC(CC(C1)OC(=O)N1NC(=CC(=N1)C(=O)OC1CC(NC(C1)(C)C)(C)C)C(=O)OC1CC(NC(C1)(C)C)(C)C)(C)C)C OIRRCMCATRAYJG-UHFFFAOYSA-N 0.000 description 1
- DYSUTBVWFJRUKW-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)(OC(=O)C)CC(=O)OC1CC(C)(C)NC(C)(C)C1 DYSUTBVWFJRUKW-UHFFFAOYSA-N 0.000 description 1
- HBUNLJQRZABWAM-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(O)(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 HBUNLJQRZABWAM-UHFFFAOYSA-N 0.000 description 1
- HAJIOQHUJLPSAL-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) benzene-1,3,5-tricarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC(C(=O)OC2CC(C)(C)NC(C)(C)C2)=CC(C(=O)OC2CC(C)(C)NC(C)(C)C2)=C1 HAJIOQHUJLPSAL-UHFFFAOYSA-N 0.000 description 1
- RBKBGHZMNFTKRE-UHFFFAOYSA-K trisodium 2-[(2-oxido-3-sulfo-6-sulfonatonaphthalen-1-yl)diazenyl]benzoate Chemical compound C1=CC=C(C(=C1)C(=O)[O-])N=NC2=C3C=CC(=CC3=CC(=C2[O-])S(=O)(=O)O)S(=O)(=O)[O-].[Na+].[Na+].[Na+] RBKBGHZMNFTKRE-UHFFFAOYSA-K 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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
- B32B17/10—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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
２枚のガラスと、前記２枚のガラス間に配置されたエチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体とエチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）とを含有するＡ膜を含む中間膜を有し、ヘイズが５０％以上９９．５％以下であり、全光線透過率が５０％以上９０％以下である合わせガラス及び合わせガラス用中間膜。Two glasses, at least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer disposed between the two glasses and an ethylene polymer ( However, it has an intermediate film including an A film containing the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer), and the haze is 50% or more and 99.5% or less. A laminated glass having a total light transmittance of 50% or more and 90% or less and an interlayer film for laminated glass.
Description
本発明の一実施態様は、合わせガラス及び合わせガラス用中間膜に関する。 One embodiment of the present invention relates to a laminated glass and an interlayer film for laminated glass.
採光窓、間仕切り、浴室ドア等には、光は透過させるが、背後にいる人及び物体は視認できない性能が要求される。このような性能を有する建材として、例えば、表面に微細な凹凸が付与されたガラス（すりガラス）や２枚の透明ガラスの間に乳白色の樹脂層（中間膜）等を有するスモーク調の合わせガラスが挙げられる。 The lighting windows, partitions, bathroom doors, and the like are required to have a performance that allows light to pass therethrough but cannot visually recognize people and objects behind them. As a building material having such a performance, for example, a smoked laminated glass having a milky white resin layer (intermediate film) or the like between a glass (ground glass) having fine irregularities on the surface or between two transparent glasses. Can be mentioned.
スモーク調の合わせガラスとして、特開昭５９−６４５５０号公報には、熱可塑性樹脂に透光性乳白剤を分散させ中間層とするものが開示されている。また、特開平７−１５７３４１号公報には、エチレン−ビニルエステル共重合体及びその変性体と非相溶性の熱可塑性ポリマーからなる組成物に二酸化チタンを添加して中間膜とするものが開示されている。
また、特開平６−２６３４８９号公報には、鹸化度の異なるポリビニルアセタール樹脂と可塑剤とからなる乳白色合わせガラス中間膜を有する乳白色合わせガラスが開示されている。As a smoked laminated glass, Japanese Patent Application Laid-Open No. 59-64550 discloses an intermediate layer in which a translucent opacifier is dispersed in a thermoplastic resin. JP-A-7-157341 discloses an intermediate film obtained by adding titanium dioxide to a composition comprising an ethylene-vinyl ester copolymer and a modified polymer incompatible with the ethylene-vinyl ester copolymer. ing.
JP-A-6-263489 discloses a milky white laminated glass having a milky white laminated glass interlayer made of a polyvinyl acetal resin and a plasticizer having different saponification degrees.
しかしながら、特開昭５９−６４５５０号公報に記載の中間層、並びに特開平７−１５７３４１号公報、及び特開平６−２６３４８９号公報に記載の中間膜は、高温高湿環境下に長時間曝されると膜等の端部から水が浸入して膜の内部の劣化が進行し、光透過性を維持することができない傾向にあった。そのため、高温高湿環境下に長時間曝されても劣化が抑制される性能（耐水性）と、光透過性及び目隠し性と、を有する合わせガラスは、提供されるに至っていないのが実情である。
なお、目隠し性とは、合わせガラスの視認側と反対側にいる人及び物体を、合わせガラスの視認側から視認できない性能を意味する。However, the intermediate layer described in JP-A-59-64550, and the intermediate films described in JP-A-7-157341 and JP-A-6-263589 are exposed to a high temperature and high humidity environment for a long time. As a result, water entered from the end of the film and the like, and deterioration inside the film progressed, and there was a tendency that light transmittance could not be maintained. Therefore, the actual situation is that a laminated glass having performance (water resistance) that suppresses deterioration even when exposed to a high temperature and high humidity environment for a long time, light transmittance and blindfold has not been provided. is there.
In addition, blindfold means the performance which cannot visually recognize the person and object which are on the opposite side to the visual recognition side of a laminated glass from the visual recognition side of a laminated glass.
本発明の一実施態様は上記に鑑みなされたものであり、以下の目的を達成することを課題とする。
すなわち、本発明の一実施態様は、光透過性、目隠し性、及び耐水性に優れた合わせガラス及び合わせガラス用中間膜を提供することを課題とする。One embodiment of the present invention has been made in view of the above, and an object thereof is to achieve the following object.
That is, it is an object of one embodiment of the present invention to provide a laminated glass and an interlayer film for laminated glass that are excellent in light transmittance, blinding property, and water resistance.
前記課題を達成するための具体的手段には、以下の態様が含まれる。
＜１＞ ２枚のガラスと、前記２枚のガラス間に配置されたエチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体とエチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）とを含有するＡ膜を含む中間膜を有し、ヘイズが５０％以上９９．５％以下であり、全光線透過率が５０％以上９０％以下である合わせガラス。
＜２＞ 前記中間膜が、エチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマーから選ばれる少なくとも１種の共重合体を含有する２つのＢ膜と、前記２つのＢ膜間に配置された前記Ａ膜とを有する少なくとも３つの膜が積層された多層構造を有する＜１＞に記載の合わせガラス。
＜３＞ 前記Ｂ膜は、さらにシランカップリング剤を含む＜２＞に記載の合わせガラス。
＜４＞ 前記エチレン・不飽和カルボン酸エステル共重合体がエチレン・（メタ）アクリル酸エステル共重合体であり、前記エチレン・ビニルエステル共重合体がエチレン・酢酸ビニル共重合体であり、前記エチレン系重合体がエチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマーから選ばれる少なくとも１種の共重合体である＜１＞〜＜３＞のいずれか１つに記載の合わせガラス。
＜５＞ 前記Ａ膜に含まれる前記エチレン・不飽和カルボン酸共重合体は、不飽和カルボン酸に由来する構成単位の含有量が共重合体の全質量に対して１質量％〜１０質量％である＜４＞に記載の合わせガラス。
＜６＞ 前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体の合計含有量が、前記エチレン・不飽和カルボン酸エステル共重合体、前記エチレン・ビニルエステル共重合体、及び前記エチレン系重合体の合計質量に対して５質量％以上４５質量％未満であり、前記エチレン系重合体の含有量が、前記エチレン・不飽和カルボン酸エステル共重合体、前記エチレン・ビニルエステル共重合体、及び前記エチレン系重合体の合計質量に対して５５質量％を超え９５質量％以下である＜１＞〜＜５＞のいずれか１つに記載の合わせガラス。
＜７＞ エチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体と、エチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）と、を含有するＡ膜を含み、厚み４００μｍにおける、ヘイズが５０％以上９９．５％以下であり、全光線透過率が５０％以上９０％以下である合わせガラス用中間膜。Specific means for achieving the above object includes the following aspects.
<1> Two glasses, at least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer disposed between the two glasses and an ethylene system An intermediate film including an A film containing a polymer (excluding the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer), and a haze of 50% or more and 99.5 %, And the total light transmittance is 50% or more and 90% or less.
<2> Two B films containing at least one copolymer selected from an ionomer of an ethylene / unsaturated carboxylic acid copolymer and an ethylene / unsaturated carboxylic acid copolymer; Laminated glass according to <1>, which has a multilayer structure in which at least three films each having the A film disposed between two B films are laminated.
<3> The laminated glass according to <2>, wherein the B film further contains a silane coupling agent.
<4> The ethylene / unsaturated carboxylic acid ester copolymer is an ethylene / (meth) acrylic acid ester copolymer, the ethylene / vinyl ester copolymer is an ethylene / vinyl acetate copolymer, and the ethylene <1> to <3>, wherein the polymer is at least one copolymer selected from ethylene / unsaturated carboxylic acid copolymers and ionomers of ethylene / unsaturated carboxylic acid copolymers Laminated glass as described.
<5> In the ethylene / unsaturated carboxylic acid copolymer contained in the A film, the content of constituent units derived from the unsaturated carboxylic acid is 1% by mass to 10% by mass with respect to the total mass of the copolymer. The laminated glass as described in <4> which is.
<6> The total content of the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer is the ethylene / unsaturated carboxylic acid ester copolymer, the ethylene / vinyl ester copolymer, And less than 45% by mass with respect to the total mass of the ethylene polymer, and the content of the ethylene polymer is the ethylene / unsaturated carboxylic acid ester copolymer or the ethylene / vinyl ester. Laminated glass according to any one of <1> to <5>, which exceeds 55% by mass and is 95% by mass or less with respect to the total mass of the copolymer and the ethylene-based polymer.
<7> At least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer, and an ethylene-based polymer (however, the ethylene / unsaturated carboxylic acid ester copolymer) And the ethylene / vinyl ester copolymer are excluded), and at a thickness of 400 μm, the haze is 50% or more and 99.5% or less, and the total light transmittance is 50% or more and 90%. The interlayer film for laminated glass as follows.
本発明の一実施態様によれば、光透過性、目隠し性、及び耐水性に優れた合わせガラス及び合わせガラス用中間膜が提供される。 According to one embodiment of the present invention, a laminated glass and an interlayer film for laminated glass that are excellent in light transmittance, blindfoldability, and water resistance are provided.
＜合わせガラス用中間膜＞
合わせガラスは、エチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体と、エチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）と、を含有するＡ膜を含む合わせガラス用中間膜（以下、単に中間膜ともいう）を有する。
中間膜は、厚み４００μｍにおける、ヘイズが５０％以上９９．５％以下であり、全光線透過率が５０％以上９０％以下である。
中間膜は、エチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマーから選ばれる少なくとも１種を含有する２つのＢ膜と、前記２つのＢ膜間に配置された前記Ａ膜と、を含む少なくとも３つの膜が積層された多層構造を有することが好ましい。<Interlayer film for laminated glass>
Laminated glass comprises at least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer, and an ethylene polymer (provided that the ethylene / unsaturated carboxylic acid ester copolymer). And an intermediate film for laminated glass (hereinafter also simply referred to as an intermediate film) including an A film containing the polymer and the ethylene / vinyl ester copolymer).
The intermediate film has a haze of 50% to 99.5% and a total light transmittance of 50% to 90% at a thickness of 400 μm.
The intermediate film is disposed between two B films containing at least one selected from ethylene / unsaturated carboxylic acid copolymer and ethylene / unsaturated carboxylic acid ionomer, and the two B films. It is preferable to have a multilayer structure in which at least three films including the A film are stacked.
本明細書における（メタ）アクリル酸は、アクリル酸及びメタクリル酸の両方を包含することを意味する。 (Meth) acrylic acid in this specification is meant to include both acrylic acid and methacrylic acid.
本発明の一実施態様の効果が現れる理由は明確ではないが、以下のように推定される。
すなわち、本発明の一実施態様は、合わせガラスの中間膜が含むＡ膜を、光透過性が高く屈折率の異なる、エチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体と、エチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）と、を含む構成とすることで、中間膜全体として、光透過性を維持したまま、両者の屈折率の差から乳白色となり、目隠し性を発現するものと考えられる。
また、Ａ膜にエチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）が含まれることで、中間膜は耐水性にも優れたものになると考えられる。The reason why the effect of the embodiment of the present invention appears is not clear, but is estimated as follows.
That is, in one embodiment of the present invention, the A film included in the interlayer film of the laminated glass is made of an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer having high light transmittance and different refractive indexes. By comprising at least one selected copolymer and an ethylene polymer (excluding the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer). As a whole, the intermediate film is thought to be milky white due to the difference in refractive index between the two while maintaining the light transmittance, and to express blindness.
In addition, since the A film contains an ethylene polymer (excluding the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer), the intermediate film has excellent water resistance. It will be a thing.
以下に、中間膜に含まれるＡ膜について、詳細に説明する。 Hereinafter, the A film included in the intermediate film will be described in detail.
≪Ａ膜≫
中間膜は、エチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体と、エチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）と、を含有するＡ膜を含む。
中間膜がＡ膜を含むことで、中間膜全体として、光透過性、目隠し性、及び耐水性に優れたものとなる。
Ａ膜は、必要に応じて、エチレン・不飽和カルボン酸エステル共重合体、エチレン・ビニルエステル共重合体、及びエチレン系重合体以外の樹脂を含んでいてもよい。≪A film≫
The interlayer film comprises at least one copolymer selected from ethylene / unsaturated carboxylic acid ester copolymer and ethylene / vinyl ester copolymer, and an ethylene-based polymer (however, the ethylene / unsaturated carboxylic acid ester copolymer). A polymer containing the polymer and the ethylene-vinyl ester copolymer).
When the intermediate film includes the A film, the entire intermediate film is excellent in light transmission, blinding, and water resistance.
The A film may contain a resin other than the ethylene / unsaturated carboxylic acid ester copolymer, the ethylene / vinyl ester copolymer, and the ethylene-based polymer as necessary.
［エチレン・不飽和カルボン酸エステル共重合体］
Ａ膜は、エチレン・不飽和カルボン酸エステル共重合体及び後述のエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体を含む。
エチレン・不飽和カルボン酸エステル共重合体は、少なくとも、エチレンに由来する構成単位と、不飽和カルボン酸エステルに由来する構成単位と、を含む。エチレン・不飽和カルボン酸エステル共重合体は、ランダム共重合体であっても、ブロック共重合体であっても、交互共重合体であってもよい。[Ethylene / unsaturated carboxylic acid ester copolymer]
The A film contains at least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer described later.
The ethylene / unsaturated carboxylic acid ester copolymer includes at least a structural unit derived from ethylene and a structural unit derived from an unsaturated carboxylic acid ester. The ethylene / unsaturated carboxylic acid ester copolymer may be a random copolymer, a block copolymer, or an alternating copolymer.
不飽和カルボン酸エステルに由来する構成単位としては、例えば、不飽和カルボン酸アルキルエステルに由来する構成単位が挙げられる。
不飽和カルボン酸エステルに由来する構成単位における不飽和カルボン酸としては、例えば、アクリル酸、メタクリル酸、エタクリル酸、クロトン酸、フマル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸等が挙げられる。
不飽和カルボン酸アルキルエステルに由来する構成単位におけるアルキル部位としては、例えば、炭素数１〜１２のアルキル基を挙げることができ、具体的には、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、セカンダリーブチル、２−エチルヘキシル、及びイソオクチル等のアルキル基を例示できる。中でも、炭素数１〜８のアルキル基が好ましい。Examples of the structural unit derived from an unsaturated carboxylic acid ester include a structural unit derived from an unsaturated carboxylic acid alkyl ester.
Examples of the unsaturated carboxylic acid in the structural unit derived from the unsaturated carboxylic acid ester include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, and the like. Can be mentioned.
Examples of the alkyl moiety in the structural unit derived from the unsaturated carboxylic acid alkyl ester include an alkyl group having 1 to 12 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n- Examples of the alkyl group include butyl, isobutyl, secondary butyl, 2-ethylhexyl, and isooctyl. Among these, an alkyl group having 1 to 8 carbon atoms is preferable.
エチレン・不飽和カルボン酸エステル共重合体としては、エチレン・（メタ）アクリル酸エステル共重合体が特に好ましい。中でも（メタ）アクリル酸エステルとして１種類の化合物に由来する構成単位を含む共重合体が好ましい。エチレン・不飽和カルボン酸エステル共重合体の例としては、エチレン・アクリル酸メチル共重合体、エチレン・アクリル酸エチル共重合体、エチレン・アクリル酸ｎ−ブチル共重合体、エチレン・アクリル酸イソブチル共重合体、エチレン・メタクリル酸メチル共重合体、エチレン・メタクリル酸エチル共重合体、エチレン・メタクリル酸ｎ−ブチル共重合体、及びエチレン・メタクリル酸イソブチル共重合体が挙げられる。 As the ethylene / unsaturated carboxylic acid ester copolymer, an ethylene / (meth) acrylic acid ester copolymer is particularly preferable. Among them, a copolymer containing a structural unit derived from one kind of compound as the (meth) acrylic acid ester is preferable. Examples of ethylene / unsaturated carboxylic acid ester copolymers include ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene / n-butyl acrylate copolymers, ethylene / isobutyl acrylate copolymers. Examples include polymers, ethylene / methyl methacrylate copolymers, ethylene / ethyl methacrylate copolymers, ethylene / n-butyl methacrylate copolymers, and ethylene / isobutyl methacrylate copolymers.
エチレンに由来する構成単位の含有量は、エチレン・不飽和カルボン酸エステル共重合体の全質量に対して４０質量％〜８０質量％であることが好ましく、５０質量％〜７０質量％であることがより好ましい。 The content of the structural unit derived from ethylene is preferably 40% by mass to 80% by mass, and 50% by mass to 70% by mass with respect to the total mass of the ethylene / unsaturated carboxylic acid ester copolymer. Is more preferable.
不飽和カルボン酸エステルに由来する構成単位の含有量は、エチレン・不飽和カルボン酸エステル共重合体全質量に対して２０質量％〜６０質量％であることが好ましく、３０質量％〜５０質量％であることがより好ましい。
不飽和カルボン酸エステルに由来する構成単位の含有量が上記範囲にあれば、中間膜のヘイズがより向上し、目隠し性と光透過性を両立できる。The content of the structural unit derived from the unsaturated carboxylic acid ester is preferably 20% by mass to 60% by mass, and preferably 30% by mass to 50% by mass with respect to the total mass of the ethylene / unsaturated carboxylic acid ester copolymer. It is more preferable that
If content of the structural unit derived from unsaturated carboxylic acid ester exists in the said range, the haze of an intermediate film will improve more and it can make blindness and light transmittance compatible.
エチレン・不飽和カルボン酸エステル共重合体は、不飽和カルボン酸エステル及びエチレン以外の他のモノマーに由来する構成単位を、本発明の一実施態様の特性を損なわない範囲で更に含んでいてもよい。ただし、その他のモノマーに由来する構成単位の含有量は不飽和カルボン酸エステルに由来する構成単位の含有量を超えないことが好ましい。 The ethylene / unsaturated carboxylic acid ester copolymer may further contain a structural unit derived from the unsaturated carboxylic acid ester and another monomer other than ethylene as long as the characteristics of one embodiment of the present invention are not impaired. . However, the content of structural units derived from other monomers preferably does not exceed the content of structural units derived from unsaturated carboxylic acid esters.
エチレン・不飽和カルボン酸エステル共重合体は、従来公知の方法で製造してもよく、市販されているものを用いてもよい。
エチレン・不飽和カルボン酸エステル共重合体は、加工性及び機械強度の観点から、１９０℃、２１６０ｇ荷重におけるメルトフローレート（ＪＩＳ−Ｋ７２１０（１９９９年））が、０．１ｇ／１０分〜１５０ｇ／１０分であることが好ましく、特に０．１ｇ／１０分〜５０ｇ／１０分であることが好ましい。The ethylene / unsaturated carboxylic acid ester copolymer may be produced by a conventionally known method, or a commercially available one may be used.
From the viewpoint of processability and mechanical strength, the ethylene / unsaturated carboxylic acid ester copolymer has a melt flow rate at 190 ° C. under a load of 2160 g (JIS-K7210 (1999)) of 0.1 g / 10 min to 150 g / It is preferably 10 minutes, and particularly preferably 0.1 g / 10 minutes to 50 g / 10 minutes.
［エチレン・ビニルエステル共重合体］
Ａ膜は、前記エチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体を含む。
エチレン・ビニルエステル共重合体は、少なくとも、エチレンに由来する構成単位と、ビニルエステルに由来する構成単位と、を含む。エチレン・ビニルエステル共重合体は、ランダム共重合体であっても、ブロック共重合体であっても、交互共重合体であってもよい。[Ethylene / vinyl ester copolymer]
The A film contains at least one copolymer selected from the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer.
The ethylene / vinyl ester copolymer includes at least a structural unit derived from ethylene and a structural unit derived from vinyl ester. The ethylene / vinyl ester copolymer may be a random copolymer, a block copolymer, or an alternating copolymer.
エチレン・ビニルエステル共重合体としては、エチレン・酪酸ビニル共重合体、エチレン・酢酸ビニル共重合体、エチレン・プロピオン酸ビニル共重合体、及びエチレン・ステアリン酸ビニル共重合体が例示され、エチレン・酢酸ビニル共重合体が好ましい。 Examples of the ethylene / vinyl ester copolymer include an ethylene / vinyl butyrate copolymer, an ethylene / vinyl acetate copolymer, an ethylene / vinyl propionate copolymer, and an ethylene / vinyl stearate copolymer. A vinyl acetate copolymer is preferred.
エチレンに由来する構成単位の含有量は、エチレン・ビニルエステル共重合体の全質量に対して４０質量％〜８０質量％であることが好ましく、５０質量％〜７０質量％であることがより好ましい。 The content of the structural unit derived from ethylene is preferably 40% by mass to 80% by mass, and more preferably 50% by mass to 70% by mass with respect to the total mass of the ethylene / vinyl ester copolymer. .
ビニルエステルに由来する構成単位の含有量は、共重合体全質量に対して２０質量％〜６０質量％であることが好ましく、３０質量％〜５０質量％であることがより好ましい。
ビニルエステルに由来する構成単位の含有量が上記範囲にあれば、中間膜のヘイズがより向上し、目隠し性と光透過性を両立できる。The content of the structural unit derived from the vinyl ester is preferably 20% by mass to 60% by mass and more preferably 30% by mass to 50% by mass with respect to the total mass of the copolymer.
If content of the structural unit derived from vinyl ester exists in the said range, the haze of an intermediate film will improve more and it can make blindness and light transmittance compatible.
エチレン・ビニルエステル共重合体は、ビニルエステル及びエチレン以外の他のモノマーに由来する構成単位を、本発明の一実施態様の特性を損なわない範囲で更に含んでいてもよい。ただし、その他のモノマーに由来する構成単位の含有量はビニルエステルに由来する構成単位の含有量を超えないことが好ましい。 The ethylene / vinyl ester copolymer may further contain a structural unit derived from a monomer other than the vinyl ester and ethylene as long as the characteristics of one embodiment of the present invention are not impaired. However, the content of structural units derived from other monomers preferably does not exceed the content of structural units derived from vinyl esters.
エチレン・ビニルエステル共重合体は従来公知の方法で製造してもよいし、市販されているものを用いてもよい。
エチレン・ビニルエステル共重合体は、加工性及び機械強度の観点から、１９０℃、２１６０ｇ荷重におけるメルトフローレート（ＪＩＳ−Ｋ７２１０（１９９９年））が、０．１ｇ／１０分〜１５０ｇ／１０分であることが好ましく、特に０．１ｇ／１０分〜５０ｇ／１０分であることが好ましい。The ethylene / vinyl ester copolymer may be produced by a conventionally known method, or a commercially available one may be used.
From the viewpoint of processability and mechanical strength, the ethylene / vinyl ester copolymer has a melt flow rate (JIS-K7210 (1999)) at 190 ° C. and 2160 g load of 0.1 g / 10 min to 150 g / 10 min. It is preferable to be 0.1 g / 10 min to 50 g / 10 min.
Ａ膜におけるエチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体の合計含有量は、エチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体、並びに後述のエチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）の合計質量に対して５０質量％以下が好ましく、５質量％以上４５質量％未満がより好ましく、１５質量％以上３５質量％以下がさらに好ましく、２０質量％以上３０質量％以下が最も好ましい。
エチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体の合計含有量が上記範囲であると、光透過性及び目隠し性に優れる。The total content of the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer in the A film is the same as the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer, 50% by mass or less is preferable with respect to the total mass of the polymer (excluding the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer), but 5% by mass or more and less than 45% by mass. Is more preferable, 15 mass% or more and 35 mass% or less is more preferable, and 20 mass% or more and 30 mass% or less is the most preferable.
When the total content of the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer is within the above range, light transmittance and blinding are excellent.
［エチレン系重合体］
Ａ膜は、エチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）を含む。
エチレン系重合体は、エチレン、プロピレン、及びブテン等の炭化水素のみを重合した単独重合体でもよく、エチレンに由来する構成単位を含み、さらに他の構成単位（以下、コモノマーに由来する構成単位ともいう）を含む共重合体でもよい。エチレン系重合体が共重合体の場合、ランダム共重合体であってもよく、ブロック共重合体であってもよく、交互共重合体であってもよい。[Ethylene polymer]
The A film contains an ethylene polymer (excluding the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer).
The ethylene polymer may be a homopolymer obtained by polymerizing only hydrocarbons such as ethylene, propylene, and butene, and includes a structural unit derived from ethylene, and further includes other structural units (hereinafter referred to as a structural unit derived from a comonomer). It may be a copolymer containing When the ethylene polymer is a copolymer, it may be a random copolymer, a block copolymer, or an alternating copolymer.
エチレン系重合体が単独重合体である場合の例としては、高密度ポリエチレン（ＨＤＰＥ）、ポリプロピレン、及びポリブテン等が挙げられる。
エチレン系重合体が共重合体である場合の例としては、エチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマー、エチレン・αオレフィン共重合体等が挙げられる。
エチレン系重合体の中でも、高密度ポリエチレン、並びにエチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマーが好ましく、エチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマーがより好ましい。Examples of the case where the ethylene polymer is a homopolymer include high density polyethylene (HDPE), polypropylene, and polybutene.
Examples of the case where the ethylene polymer is a copolymer include ethylene / unsaturated carboxylic acid copolymers, ionomers of ethylene / unsaturated carboxylic acid copolymers, ethylene / α-olefin copolymers, and the like.
Among ethylene polymers, high density polyethylene, and ionomers of ethylene / unsaturated carboxylic acid copolymers and ethylene / unsaturated carboxylic acid copolymers are preferred, ethylene / unsaturated carboxylic acid copolymers and ethylene / unsaturated copolymers. Ionomer of carboxylic acid copolymer is more preferable.
エチレン系重合体が共重合体の場合、コモノマーに由来する構成単位としては、例えば、プロピレン、ブテン、及びオクテン等のα−オレフィンに由来する構成単位、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、及び無水マレイン酸モノエステル等の不飽和カルボン酸に由来する構成単位が挙げられる。中でも（メタ）アクリル酸に由来する構成単位が好ましく、メタクリル酸に由来する構成単位がより好ましい。 When the ethylene polymer is a copolymer, examples of the structural unit derived from a comonomer include a structural unit derived from an α-olefin such as propylene, butene, and octene, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride. Examples include acid and structural units derived from unsaturated carboxylic acids such as maleic anhydride monoester. Among these, a structural unit derived from (meth) acrylic acid is preferable, and a structural unit derived from methacrylic acid is more preferable.
エチレン系重合体が共重合体の場合、エチレンに由来する構成単位の含有量は、エチレン系重合体の全質量に対して７５質量％〜９９質量％が好ましく、８０質量％〜９９質量％がより好ましく、９０質量％〜９９質量％がさらに好ましい。 When the ethylene polymer is a copolymer, the content of the structural unit derived from ethylene is preferably 75% by mass to 99% by mass, and 80% by mass to 99% by mass with respect to the total mass of the ethylene polymer. More preferably, 90 mass%-99 mass% is further more preferable.
エチレン系重合体が共重合体の場合、コモノマーに由来する構成単位の含有量は、エチレン系重合体の全質量に対して１質量％〜２５質量％が好ましく、１質量％〜２０質量％がより好ましく、１質量％〜１０質量％がさらに好ましい。
コモノマーに由来する構成単位の含有量が上記範囲内であると、エチレン系重合体の耐水性、耐熱性がより向上し、かつ目隠し性と光透過性を両立できる。When the ethylene polymer is a copolymer, the content of the structural unit derived from the comonomer is preferably 1% by mass to 25% by mass with respect to the total mass of the ethylene polymer, and 1% by mass to 20% by mass. More preferably, 1% by mass to 10% by mass is even more preferable.
When the content of the structural unit derived from the comonomer is within the above range, the water resistance and heat resistance of the ethylene polymer are further improved, and both blinding and light transmittance can be achieved.
エチレン系重合体がエチレン・不飽和カルボン酸共重合体である場合、エチレン・不飽和カルボン酸共重合体は、エチレンに由来する構成単位及び不飽和カルボン酸に由来する構成単位の合計１００質量％に対し、０質量％を超えて３０質量％以下の範囲（好ましくは０質量％を超えて２５質量％以下の範囲）で、その他の共重合性モノマーに由来する構成単位を含んでもよい。ただし、その他の共重合性モノマーに由来する構成単位の含有量は不飽和カルボン酸に由来する構成単位の含有量を超えないことが好ましい。 When the ethylene-based polymer is an ethylene / unsaturated carboxylic acid copolymer, the ethylene / unsaturated carboxylic acid copolymer is 100% by mass in total of the structural unit derived from ethylene and the structural unit derived from unsaturated carboxylic acid. On the other hand, a structural unit derived from another copolymerizable monomer may be included in the range of more than 0% by mass and 30% by mass or less (preferably in the range of more than 0% by mass and 25% by mass or less). However, the content of structural units derived from other copolymerizable monomers preferably does not exceed the content of structural units derived from unsaturated carboxylic acids.
その他の共重合性モノマーとしては、不飽和エステル、例えば、酢酸ビニル及びプロピオン酸ビニル等のビニルエステル；アクリル酸メチル、アクリル酸エチル、アクリル酸イソブチル、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、メタクリル酸メチル及びメタクリル酸イソブチル等の（メタ）アクリル酸アルキルエステルなどが挙げられる。その他の共重合体モノマーに由来する構成単位を上記範囲で含むことにより、エチレン・不飽和カルボン酸共重合体の柔軟性が向上するため好ましい。 Other copolymerizable monomers include unsaturated esters such as vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, Examples include (meth) acrylic acid alkyl esters such as methyl methacrylate and isobutyl methacrylate. It is preferable to include structural units derived from other copolymer monomers in the above range because the flexibility of the ethylene / unsaturated carboxylic acid copolymer is improved.
エチレン系重合体としては、エチレン・不飽和カルボン酸共重合体のアイオノマーを用いることができる。アイオノマーは、エチレン・不飽和カルボン酸共重合体中のカルボン酸基を金属で中和したものである。
カルボン酸基を中和する金属としては、リチウム及びナトリウムなどのアルカリ金属；カルシウム、マグネシウム、亜鉛及びアルミニウムなどの多価金属などが挙げられる。As the ethylene polymer, an ionomer of an ethylene / unsaturated carboxylic acid copolymer can be used. The ionomer is obtained by neutralizing a carboxylic acid group in an ethylene / unsaturated carboxylic acid copolymer with a metal.
Examples of the metal that neutralizes the carboxylic acid group include alkali metals such as lithium and sodium; polyvalent metals such as calcium, magnesium, zinc, and aluminum.
アイオノマーにおけるエチレンに由来する構成単位及び不飽和カルボン酸単量体に由来する構成単位の含有量の好ましい範囲は、上記のエチレン系重合体におけるエチレンに由来する構成単位の含有量及びコモノマーに由来する構成単位の含有量と同じである。 The preferable range of the content of the structural unit derived from ethylene and the structural unit derived from the unsaturated carboxylic acid monomer in the ionomer is derived from the content of the structural unit derived from ethylene and the comonomer in the ethylene polymer. It is the same as the content of the structural unit.
アイオノマーの中和度は、通常８０％以下が好ましい。中和度が８０％以下であると、光透過性と目隠し性とが両立した中間膜を得ることができる。一般的に、中和度は６０％以下がより好ましく、３０％以下が更に好ましい。中和度の下限は、１０％が好ましい。 The neutralization degree of the ionomer is usually preferably 80% or less. When the degree of neutralization is 80% or less, it is possible to obtain an intermediate film having both light transmittance and blinding properties. In general, the degree of neutralization is more preferably 60% or less, and further preferably 30% or less. The lower limit of the degree of neutralization is preferably 10%.
上記のエチレン系重合体は、各重合成分を高温及び高圧下でラジカル共重合することで得ることができる。また、エチレン・不飽和カルボン酸共重合体のアイオノマーは、エチレン・不飽和カルボン酸共重合体と金属化合物を反応させることによって得ることができる。 The ethylene polymer can be obtained by radical copolymerization of each polymerization component at high temperature and high pressure. An ionomer of an ethylene / unsaturated carboxylic acid copolymer can be obtained by reacting an ethylene / unsaturated carboxylic acid copolymer with a metal compound.
エチレン系重合体は、加工性及び機械強度の観点から、１９０℃、２１６０ｇ荷重におけるメルトフローレート（ＭＦＲ）（ＪＩＳ−Ｋ７２１０（１９９９年））が、０．１ｇ／１０分〜１５０ｇ／１０分であることが好ましく、特に０．１ｇ／１０分〜５０ｇ／１０分であることが好ましい。 The ethylene polymer has a melt flow rate (MFR) at 190 ° C. and a load of 2160 g (JIS-K7210 (1999)) of 0.1 g / 10 min to 150 g / 10 min from the viewpoint of processability and mechanical strength. It is preferable to be 0.1 g / 10 min to 50 g / 10 min.
Ａ膜におけるエチレン系重合体の含有量は、エチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体、並びにエチレン系重合体の合計質量に対して５０質量％以上が好ましく、５５質量％を超え９５質量％以下がより好ましく、６５質量％以上８５質量％以下がさらに好ましく、７０質量％以上８０質量％以下が最も好ましい。 The content of the ethylene polymer in the A film is preferably 50% by mass or more based on the total mass of the ethylene / unsaturated carboxylic acid ester copolymer, the ethylene / vinyl ester copolymer, and the ethylene polymer, More than 95 mass% and more than 95 mass% is more preferable, 65 mass% or more and 85 mass% or less are more preferable, and 70 mass% or more and 80 mass% or less are the most preferable.
［その他の樹脂］
Ａ膜は、本発明の一実施態様の目的を損なわない範囲内においてその他の樹脂を含んでもよい。
その他の樹脂としては、例えば、ポリプロピレン、ポリブテン、ポリイソプレン、ポリクロロプレンが挙げられる。[Other resins]
The A film may contain other resins as long as the object of one embodiment of the present invention is not impaired.
Examples of other resins include polypropylene, polybutene, polyisoprene, and polychloroprene.
［その他の添加剤］
Ａ膜は、本発明の一実施態様の目的を損なわない範囲内において、各種添加剤を含んでもよい。かかる添加剤としては、例えば、架橋剤、架橋助剤、紫外線吸収剤、光安定剤、酸化防止剤及びシランカップリング剤が挙げられる。[Other additives]
A film | membrane may contain various additives in the range which does not impair the objective of one embodiment of this invention. Examples of such additives include a crosslinking agent, a crosslinking assistant, an ultraviolet absorber, a light stabilizer, an antioxidant, and a silane coupling agent.
架橋剤としては、半減期１時間の分解温度が通常９０℃〜１８０℃、好ましくは１００℃〜１５０℃の有機過酸化物を用いることが好ましい。このような有機過酸化物としては、例えば、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシ−２−エチルヘキシルカーボネート、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシベンゾエート、ジクミルパーオキサイド、２，５−ジメチル−２，５−ビス（ｔ−ブチルパーオキシ）ヘキサン、ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ビス（ｔ−ブチルパーオキシ）ヘキシン−３、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、メチルエチルケトンパーオキサイド、２，５−ジメチルヘキシル−２，５−ビスパーオキシベンゾエート、ｔ−ブチルハイドロパーオキサイド、ｐ−メンタンハイドロパーオキサイド、ベンゾイルパーオキサイド、ｐ−クロルベンゾイルパーオキサイド、ｔ−ブチルパーオキシイソブチレート、ヒドロキシヘプチルパーオキサイド及びジクロヘキサノンパーオキサイドなどが挙げられる。
Ａ膜における架橋剤の含有量は、エチレン系重合体１００質量部に対し、０．１質量部〜５質量部が好ましく、０．５質量部〜３質量部がより好ましい。As a crosslinking agent, it is preferable to use an organic peroxide having a decomposition temperature of 90 ° C. to 180 ° C., preferably 100 ° C. to 150 ° C., with a half-life of 1 hour. Examples of such organic peroxides include t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyacetate, t-butyl peroxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, Methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate t-butyl hydroperoxide, p- menthane hydroperoxide, benzoyl peroxide, p- chlorobenzoyl peroxide, t- butyl peroxy isobutyrate, etc. hydroxyheptyl peroxide and di cyclohexanone peroxide.
0.1 mass part-5 mass parts are preferable with respect to 100 mass parts of ethylene-type polymers, and, as for content of the crosslinking agent in A film | membrane, 0.5 mass part-3 mass parts are more preferable.
架橋助剤としては、例えば、多不飽和化合物が挙げられる。多不飽和化合物としては、トリアリルイソシアヌレート、トリアリルシアヌレート、ジアリルフタレート、ジアリルフマレート及びジアリルマレエートなどのポリアリル化合物；エチレングリコールジアクリレート、エチレングリコールジメタクリレート及びトリメチロールプロパントリメタクリレートなどのポリ（メタ）アクリロキシ化合物；ジビニルベンゼンなどが挙げられる。
Ａ膜における架橋助剤の含有量は、エチレン系重合体１００質量部に対し、５質量部以下が好ましく、０．１質量部〜３質量部がより好ましい。Examples of the crosslinking aid include polyunsaturated compounds. Polyunsaturated compounds include polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate and diallyl maleate; polyalkylenes such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate (Meth) acryloxy compounds; divinylbenzene and the like.
5 mass parts or less are preferable with respect to 100 mass parts of ethylene-type polymers, and, as for content of the crosslinking adjuvant in A film | membrane, 0.1 mass part-3 mass parts are more preferable.
紫外線吸収剤としては、例えば、２−ヒドロキシ−４−メトキシベンゾフェノン、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−２−カルボキシベンゾフェノン及び２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノンなどのベンゾフェノン系紫外線吸収剤；２−（２’−ヒドロキシ−３’，５’−ジｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾール及び２−（２’−ヒドロキシ−５−ｔ−オクチルフェニル）ベンゾトリアゾールなどのベンゾトリアゾール系紫外線吸収剤；フェニルサリチレート及びｐ−オクチルフェニルサリチレートなどのサリチル酸エステル系紫外線吸収剤が挙げられる。 Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone and 2-hydroxy-4-n-. Benzophenone ultraviolet absorbers such as octoxybenzophenone; 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5-methylphenyl) benzotriazole and Examples include benzotriazole ultraviolet absorbers such as 2- (2′-hydroxy-5-t-octylphenyl) benzotriazole; salicylic acid ester ultraviolet absorbers such as phenyl salicylate and p-octylphenyl salicylate.
光安定剤としては、例えば、ヒンダードアミン系光安定剤が挙げられる。
ヒンダードアミン系光安定剤として、例えば、４−アセトキシ−２，２，６，６−テトラメチルピペリジン、４−ステアロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン、４−シクロヘキサノイルオキシ−２，２，６，６−テトラメチルピペリジン、４−（ｏ−クロロベンゾイルオキシ）−２，２，６，６−テトラメチルピペリジン、４−（フェノキシアセトキシ）−２，２，６，６−テトラメチルピペリジン、１，３，８−トリアザ−７，７，９，９−テトラメチル−２，４−ジオキソ−３−ｎオクチル−スピロ［４，５］デカン、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（２，２，６，６−テトラメチル−４−ピペリジル）テレフタレート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、トリス（２，２，６，６−テトラメチル−４−ピペリジル）ベンゼン−１，３，５−トリカルボキシレート、トリス（２，２，６，６−テトラメチル−４−ピペリジル）−２−アセトキシプロパン−１，２，３−トリカルボキシレート、トリス（２，２，６，６−テトラメチル−４−ピペリジル）−２−ヒドロキシプロパン−１，２，３−トリカルボキシレート、トリス（２，２，６，６−テトラメチル−４−ピペリジル）トリアジン−２，４，６−トリカルボキシレート、トリス（２，２，６，６−テトラメチル−４−ピペリジン）ホスファイト、トリス（２，２，６，６−テトラメチル−４−ピペリジル）ブタン−１，２，３−トリカルボキシレート、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）プロパン−１，１，２，３−テトラカルボキシレート、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）ブタン−１，２，３，４−テトラカルボキシレートが挙げられる。Examples of the light stabilizer include hindered amine light stabilizers.
Examples of hindered amine light stabilizers include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2 , 6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexanoyloxy-2,2,6,6-tetramethylpiperidine, 4- (o- Chlorobenzoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenoxyacetoxy) -2,2,6,6-tetramethylpiperidine, 1,3,8-triaza-7,7,9, 9-tetramethyl-2,4-dioxo-3-noctyl-spiro [4,5] decane, bis (2,2,6,6-tetramethyl-4-piperidyl) Bacate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Tris (2,2,6,6 -Tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-acetoxypropane-1,2,3-tri Carboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-hydroxypropane-1,2,3-tricarboxylate, tris (2,2,6,6-tetramethyl-4 -Piperidyl) triazine-2,4,6-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidine) phosphite, tris (2,2,6,6- Tramethyl-4-piperidyl) butane-1,2,3-tricarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) propane-1,1,2,3-tetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate.
酸化防止剤としては、例えば、各種ヒンダードフェノール系酸化防止剤及びホスファイト系酸化防止剤が挙げられる。
ヒンダードフェノール系酸化防止剤の具体例としては、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、２−ｔ−ブチル−４−メトキシフェノール、３−ｔ−ブチル−４−メトキシフェノール、２，６−ジ−ｔ−ブチル−４−エチルフェノール、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４’−メチレンビス（２，６−ジ−ｔ−ブチルフェノール）、２，２’−メチレンビス［６−（１−メチルシクロヘキシル）−ｐ−クレゾール］、ビス［３,３−ビス（４−ヒドロキシ−３−ｔ−ブチルフェニル）ブチリックアシッド］グリコールエステル、４，４’−ブチリデンビス（６−ｔ−ブチル−ｍ−クレゾール）、２，２’−エチリデンビス（４−ｓｅｃ−ブチル−６−ｔ−ブチルフェノール）、２，２’−エチリデンビス（４，６−ジ−ｔ−ブチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−２，４，６−トリメチルベンゼン、２，６−ジフェニル−４−オクタデシロキシフェノール、テトラキス［メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン、ｎ−オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、４，４’−チオビス（６−ｔ−ブチル−ｍ−クレゾール）、トコフェロール、３，９−ビス［１，１−ジメチル−２−［β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］エチル］２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルチオ）−１，３，５−トリアジンなどが挙げられる。
また、ホスファイト系酸化防止剤の具体例としては、３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルフォスファネートジメチルエステル、ビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファネートなどが挙げられる。
Ａ膜における酸化防止剤、光安定剤及び紫外線吸収剤の含有量は、Ａ膜の全質量を１００質量部としたときに、各々５質量部以下が好ましく、０．１質量部〜３質量部がより好ましい。Examples of the antioxidant include various hindered phenol-based antioxidants and phosphite-based antioxidants.
Specific examples of the hindered phenol antioxidant include 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2 , 6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-methylenebis (2,6-di-t-butylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], bis [3,3-bis (4-hydroxy) -3-t-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-t-butyl-m-cresol), 2,2′-ethylidenebis (4-sec) -Butyl-6-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) Phenyl) butane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2,6-diphenyl-4-octadecyloxyphenol, Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4′-thiobis (6-tert-butyl-m-cresol), tocopherol, 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzylthio ) -1,3,5-triazine and the like.
Specific examples of phosphite antioxidants include 3,5-di-tert-butyl-4-hydroxybenzyl phosphinate dimethyl ester, bis (3,5-di-tert-butyl-4-hydroxybenzyl). Examples thereof include ethyl phosphonate and tris (2,4-di-t-butylphenyl) phosphanate.
The content of the antioxidant, light stabilizer and ultraviolet absorber in the A film is preferably 5 parts by mass or less, and 0.1 to 3 parts by mass when the total mass of the A film is 100 parts by mass. Is more preferable.
シランカップリング剤としては、ビニル基、アミノ基又はエポキシ基と、アルコキシ基などの加水分解基と、を有するシランカップリング剤、並びにチタネート系カップリング剤が挙げられる。
シランカップリング剤の具体例としては、ビニルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルメチルジエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプピルトリメトキシシラン及びＮ−フェニル−３−アミノプロピルトリエトキシシランなどが挙げられる。
Ａ膜におけるシランカップリング剤の含有量は、Ａ膜の全質量を１００質量部としたときに、５質量部以下が好ましく、０．０２質量部〜３質量部がより好ましい。シランカップリング剤が上記範囲で含まれていると、後述するガラスシートとＡ膜との接着性を向上させることができる。Examples of the silane coupling agent include a silane coupling agent having a vinyl group, an amino group or an epoxy group, and a hydrolyzing group such as an alkoxy group, and a titanate coupling agent.
Specific examples of the silane coupling agent include vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxy. Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyl Examples include diethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.
The content of the silane coupling agent in the A film is preferably 5 parts by mass or less, more preferably 0.02 to 3 parts by mass when the total mass of the A film is 100 parts by mass. When the silane coupling agent is contained in the above range, adhesion between a glass sheet and an A film described later can be improved.
また、Ａ膜には、上述した添加剤以外に、必要に応じて、着色剤、光拡散剤、難燃剤及び金属不活性剤などの添加剤を含有させることができる。
着色剤としては、顔料（無機顔料、有機顔料）、染料等が挙げられる。これらの着色剤は公知の種々のものから選択できる。In addition to the additives described above, the A film can contain additives such as a colorant, a light diffusing agent, a flame retardant, and a metal deactivator as necessary.
Examples of the colorant include pigments (inorganic pigments, organic pigments), dyes, and the like. These colorants can be selected from various known ones.
無機顔料としては、例えば、二酸化チタン、亜鉛華、鉛白、リトポン、バライト、沈降性硫酸バリウム、炭酸カルシウム、せっこう、沈降性シリカ等の白色無機顔料、カーボンブラック、ランプブラック、チタンブラック、合成鉄黒等の黒色無機顔料、亜鉛末、亜酸化鉛、スレート粉等の灰色無機顔料、カドミウム赤、カドミウム水銀赤、銀朱、べんがら、モリブテン赤、鉛丹等の赤色無機顔料、アンバー、酸化鉄茶等の褐色無機顔料、カドミウム黄、亜鉛黄、オーカ、シエナ、合成オーカ、黄鉛、チタン黄等の黄色無機顔料、酸化クロム緑、コバルト緑、クロム緑等の緑色無機顔料、群青、紺青、鉄青、コバルト青等の青色無機顔料、金属粉無機顔料が挙げられる。 Examples of inorganic pigments include titanium dioxide, zinc white, lead white, lithopone, barite, precipitated barium sulfate, calcium carbonate, gypsum, and precipitated silica, white inorganic pigments, carbon black, lamp black, titanium black, synthetic Black inorganic pigments such as iron black, gray inorganic pigments such as zinc powder, lead suboxide, slate powder, red inorganic pigments such as cadmium red, cadmium mercury red, silver vermilion, red rose, molybten red, red lead, amber, iron oxide tea Brown inorganic pigments such as cadmium yellow, zinc yellow, ocher, sienna, synthetic ocher, yellow inorganic pigments such as yellow lead, titanium yellow, green inorganic pigments such as chromium oxide green, cobalt green, chromium green, ultramarine blue, bitumen, iron Examples include blue inorganic pigments such as blue and cobalt blue, and metal powder inorganic pigments.
有機顔料としては、例えば、パーマネント・レッド４Ｒ、パラ・レッド、ファースト・エローＧ、ファースト・エロー１０Ｇ、ジスアゾ・エローＧ、ジスアゾ・エローＧＲ、ジスアゾ・オレンジ、ピラゾロン・オレンジ、ブリリアント・カーミン３Ｂ、ブリリアント・カーミン６Ｂ、ブリリアント・スカーレットＧ、ブリリアント・ボルドー１０Ｂ、ボルドー５Ｂ、パーマネント・レッドＦ５Ｒ、パーマネント・カーミンＦＢ、リソール・レッドＲ、リソール・レッドＢ、レーキ・レッドＣ、レーキ・レッドＤ、ブリリアント・ファスト・スカーレット、ピラゾロン・レッド、ボン・マルーン・ライト、ボン・マルーン・メジアム、ファイア・レッド等のアゾ顔料、ナフトール・グリーンＢ等のニトロソ顔料、ナフトール・エローＳ等のニトロ顔料、ローダミンＢレーキ、ローダミン６Ｇレーキ等の塩基性染料系レーキ、アリザリン・レーキ等の媒染染料系レーキ、インダンスレン・ブルー等の建染染料系顔料、フタロシアニン・ブルー、フタロシアニン・グリーン、ファスト・スカイ・ブルー等のフタロシアニン顔料、ジオキサジンバイオレット等のジオキサジン系顔料が挙げられる。
この他にも、有機蛍光顔料やパール顔料などが使用可能である。Examples of organic pigments include Permanent Red 4R, Para Red, First Yellow G, First Yellow 10G, Disazo Yellow G, Disazo Yellow GR, Disazo Orange, Pyrazolone Orange, Brilliant Carmine 3B, Brilliant Carmine 6B, Brilliant Scarlet G, Brilliant Bordeaux 10B, Bordeaux 5B, Permanent Red F5R, Permanent Carmine FB, Risole Red R, Risole Red B, Rake Red C, Rake Red D, Brilliant Fast・ Azo pigments such as Scarlet, Pyrazolone Red, Bon Maroon Light, Bon Maroon Medium, Fire Red, Nitroso Pigments such as Naphthol Green B, Nito such as Naphthol Yellow S Pigments, basic dyes such as rhodamine B lake and rhodamine 6G lake, mordant dyes such as alizarin and lake, vat dyes such as indanthrene blue, phthalocyanine blue, phthalocyanine green, fast Examples thereof include phthalocyanine pigments such as sky blue and dioxazine pigments such as dioxazine violet.
In addition, organic fluorescent pigments and pearl pigments can be used.
光拡散剤としては、無機系球状物質及び有機系球状物質が挙げられる。無機系球状物質としては、例えば、ガラスビーズ、シリカビーズ、シリコンアルコキシドビーズ、中空ガラスビーズが挙げられる。有機系球状物質としては、例えば、アクリル系ビーズ及びビニルベンゼン系ビーズなどのプラスチックビーズが挙げられる。 Examples of the light diffusing agent include inorganic spherical materials and organic spherical materials. Examples of the inorganic spherical material include glass beads, silica beads, silicon alkoxide beads, and hollow glass beads. Examples of the organic spherical material include plastic beads such as acrylic beads and vinylbenzene beads.
難燃剤としては、臭素化物などのハロゲン系難燃剤、リン系難燃剤、シリコーン系難燃剤、並びに水酸化マグネシウム、及び水酸化アルミニウムなどの金属水和物などが挙げられる。 Examples of the flame retardant include halogen-based flame retardants such as bromides, phosphorus-based flame retardants, silicone-based flame retardants, and metal hydrates such as magnesium hydroxide and aluminum hydroxide.
金属不活性剤としては、熱可塑性樹脂の金属害を抑制する化合物として周知のものから選択できる。金属不活性剤は、二種以上を併用してもよい。金属不活性剤の好ましい例としては、ヒドラジド誘導体、及びトリアゾール誘導体を挙げることができる。
ヒドラジド誘導体としては、デカメチレンジカルボキシル−ジサリチロイルヒドラジド、２’，３−ビス［３−［３，５−ジーｔｅｒｔ−ブチル−４−ヒドロキシフェニル］プロピオニル］プロピオノヒドラジド、及びイソフタル酸ビス（２−フェノキシプロピオニル−ヒドラジド）が好適に挙げられる。
トリアゾール誘導体としては、３−（Ｎ−サリチロイル）アミノ−１，２，４−トリアゾールが好適に挙げられる。
ヒドラジド誘導体、及びトリアゾール誘導体以外にも、金属不活性剤として、２，２’−ジヒドロキシ−３，３’−ジ−（α−メチルシクロヘキシル）−５，５’−ジメチル・ジフェニルメタン、トリス−（２−メチル−４−ヒドロキシ−５−第三−ブチルフェニル）ブタン、２−メルカプトベンズイミダゾールとフェノール縮合物との混合物などが挙げられる。As a metal deactivator, it can select from the well-known thing as a compound which suppresses the metal damage of a thermoplastic resin. Two or more metal deactivators may be used in combination. Preferable examples of the metal deactivator include hydrazide derivatives and triazole derivatives.
Examples of hydrazide derivatives include decamethylene dicarboxyl-disalicyloyl hydrazide, 2 ′, 3-bis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl] propionohydrazide, and bisisophthalate. (2-phenoxypropionyl-hydrazide) is preferably mentioned.
Preferred examples of the triazole derivative include 3- (N-salicyloyl) amino-1,2,4-triazole.
In addition to hydrazide derivatives and triazole derivatives, 2,2′-dihydroxy-3,3′-di- (α-methylcyclohexyl) -5,5′-dimethyl diphenylmethane, tris- (2 -Methyl-4-hydroxy-5-tert-butylphenyl) butane, a mixture of 2-mercaptobenzimidazole and a phenol condensate.
≪その他の層≫
中間膜は、少なくとも、前記Ａ膜とその他の膜とが積層された多層構造を有していてもよい。
中間膜が多層構造を有する場合、中間層は、少なくともＡ膜を含み、厚み４００μｍにおける、ヘイズが５０％以上９９．５％以下であり、全光線透過率が５０％以上９０％以下であれば、Ａ膜に積層するその他の膜の材質は特に制限されない。
その他の膜としては、中間膜の耐水性の観点から、エチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマーから選ばれる少なくとも１種の共重合体を含有する膜が好ましい。
中間膜のより好ましい態様としては、エチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマーから選ばれる少なくとも１種の共重合体を含有する２つのＢ膜と、２つのＢ膜間に配置された前記Ａ膜を含む少なくとも３つの膜が積層された多層構造を有する態様が挙げられる。≪Other layers≫
The intermediate film may have a multilayer structure in which at least the A film and other films are laminated.
When the intermediate film has a multilayer structure, the intermediate layer includes at least the A film, and has a haze of 50% to 99.5% and a total light transmittance of 50% to 90% at a thickness of 400 μm. The material of other films laminated on the A film is not particularly limited.
The other film is a film containing at least one copolymer selected from ethylene / unsaturated carboxylic acid copolymer and ionomer of ethylene / unsaturated carboxylic acid copolymer from the viewpoint of water resistance of the intermediate film. Is preferred.
As a more preferable embodiment of the intermediate film, two B films containing at least one copolymer selected from ethylene / unsaturated carboxylic acid copolymer and ethylene / unsaturated carboxylic acid copolymer ionomer, An embodiment having a multilayer structure in which at least three films including the A film disposed between two B films is laminated.
Ｂ膜に含まれるエチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマーとしては、前記Ａ膜で説明したエチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマーが挙げられる。
また、Ｂ膜は前記その他の樹脂及びその他の添加剤を含んでいてもよい。
Ｂ膜は、ヘイズが４０％以上であることが好ましく、６０％以上であることがより好ましく、８０％以上であることがさらに好ましい。Examples of the ionomer of the ethylene / unsaturated carboxylic acid copolymer and the ethylene / unsaturated carboxylic acid copolymer contained in the B film include the ethylene / unsaturated carboxylic acid copolymer and the ethylene / unsaturated carboxylic acid copolymer described in the A film. An ionomer of an acid copolymer can be mentioned.
Further, the B film may contain the other resin and other additives.
The B film preferably has a haze of 40% or more, more preferably 60% or more, and still more preferably 80% or more.
［中間膜の物性］
中間膜は、厚み４００μｍにおける、ヘイズが５０％以上９９．５％以下であり、全光線透過率が５０％以上９０％以下である。ヘイズ及び全光線透過率が上記範囲であることによって、合わせガラスのヘイズを５０％以上９９．５％以下にすることができ、全光線透過率を５０％以上９０％以下にすることができる。[Physical properties of interlayer film]
The intermediate film has a haze of 50% to 99.5% and a total light transmittance of 50% to 90% at a thickness of 400 μm. When the haze and the total light transmittance are within the above ranges, the haze of the laminated glass can be 50% or more and 99.5% or less, and the total light transmittance can be 50% or more and 90% or less.
中間膜の厚み４００μｍにおけるヘイズが５０％以上であると合わせガラスは目隠し性に優れ、９９．５％以下であると合わせガラスは光透過性に優れる。
中間膜の厚み４００μｍにおけるヘイズは、６０％以上９９．５％以下が好ましく、８０％以上９９．５％以下がより好ましく、８５％以上９９．５％以下が更に好ましく、９０％以上９９％が最も好ましい。When the haze at an intermediate film thickness of 400 μm is 50% or more, the laminated glass has excellent blinding properties, and when it is 99.5% or less, the laminated glass has excellent light transmittance.
The haze at an interlayer thickness of 400 μm is preferably 60% or more and 99.5% or less, more preferably 80% or more and 99.5% or less, still more preferably 85% or more and 99.5% or less, and 90% or more and 99%. Most preferred.
中間膜の厚み４００μｍにおける全光線透過率が５０％以上であると合わせガラスは光透過性に優れ、９０％を以下であると合わせガラスは目隠し性に優れる。
中間膜の厚み４００μｍにおける全光線透過率は、６０％以上９０％以下が好ましく、７０％以上９０％以下がより好ましく、７５％以上８５％以下が最も好ましい。When the total light transmittance at an intermediate film thickness of 400 μm is 50% or more, the laminated glass is excellent in light transmittance, and when it is 90% or less, the laminated glass is excellent in blinding.
The total light transmittance at a thickness of 400 μm of the interlayer film is preferably 60% or more and 90% or less, more preferably 70% or more and 90% or less, and most preferably 75% or more and 85% or less.
ヘイズは、ＪＩＳ−Ｋ７１３６：２０００、全光線透過率は、ＪＩＳ−Ｋ７３６１：１９９７に準じて測定された値である。 The haze is a value measured according to JIS-K7136: 2000, and the total light transmittance is measured according to JIS-K7361: 1997.
［中間膜の成形］
中間膜の成形は、単層Ｔ−ダイ押出機、多層Ｔ−ダイ押出機、カレンダー成形機、単層インフレーション成形機、多層インフレーション成形機などを用いた公知の方法によって行なうことができる。[Formation of interlayer film]
The intermediate film can be formed by a known method using a single layer T-die extruder, a multilayer T-die extruder, a calendering machine, a single layer inflation molding machine, a multilayer inflation molding machine, or the like.
例えば、中間膜がＡ膜のみで形成される場合、原料であるエチレン・不飽和カルボン酸共重合体及びエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体、並びにエチレン系重合体に、必要に応じ、酸化防止剤、光安定剤、紫外線吸収剤及びシランカップリング剤等の添加剤を添加してドライブレンドし、Ｔ−ダイ押出機のホッパーから供給し、シート状に押出成形することにより得られる。
中間膜がＡ膜のみで形成される場合、中間膜の厚みは、１０μｍ〜５０００μｍが好ましく、５０μｍ〜２０００μｍがより好ましい。For example, when the intermediate film is formed only of the A film, at least one copolymer selected from an ethylene / unsaturated carboxylic acid copolymer and an ethylene / vinyl ester copolymer as raw materials, and an ethylene polymer If necessary, add additives such as antioxidants, light stabilizers, UV absorbers, and silane coupling agents, dry blend, feed from the hopper of the T-die extruder, and extrude into sheets Can be obtained.
When the intermediate film is formed only of the A film, the thickness of the intermediate film is preferably 10 μm to 5000 μm, and more preferably 50 μm to 2000 μm.
例えば、中間膜が多層構造を有する場合、その他の膜は、前記Ａ膜と同様の方法で成形することができ、成形したのち真空加熱貼合器等を用いてＡ膜と貼り合わせてもよい。また、その他の膜は、多層押出機を用いてＡ膜と一体成形して多層構造を有する中間膜を成形してもよい。
その他の膜の厚みは、５μｍ〜１０００μｍが好ましく、１０μｍ〜５００μｍがより好ましい。For example, when the intermediate film has a multilayer structure, the other films can be formed by the same method as the A film, and after forming, the film may be bonded to the A film using a vacuum heat bonding machine or the like. . Further, the other film may be integrally formed with the A film using a multilayer extruder to form an intermediate film having a multilayer structure.
The thickness of the other film is preferably 5 μm to 1000 μm, more preferably 10 μm to 500 μm.
中間膜が、２つのＢ膜と、２つのＢ膜間に配置された前記Ａ膜と、を含む少なくとも３つの膜が積層された多層構造を有する場合、各Ｂ膜の厚みが１０μｍ〜２００μｍであり、Ａ膜の厚みが４０μｍ〜１８００μｍであることが好ましい。 When the intermediate film has a multilayer structure in which at least three films including two B films and the A film disposed between the two B films are stacked, the thickness of each B film is 10 μm to 200 μm. The thickness of the A film is preferably 40 μm to 1800 μm.
＜合わせガラス＞
合わせガラスは、２枚のガラスと、前記２枚のガラス間に配置されたエチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体と、エチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）と、を含有するＡ膜を含む中間膜（既述の中間膜）を有する。
また、合わせガラスは、ヘイズが５０％以上９９.５％以下であり、全光線透過率が５０％以上９０％以下である。
ヘイズが５０％未満であると目隠し性に劣り、９９.５％を超えると光透過性に劣る。ヘイズは、６０％以上９９．５％以下が好ましく、８０％以上９９．５％以下がより好ましく、８５％以上９９．５％以下がさらに好ましく、９０％以上９９．５％以下がさらに好ましく、９０％以上９９％以下が最も好ましい。
全光線透過率が５０％未満であると光透過性に劣り、９０％を超えると目隠し性に劣る。全光線透過率は、６０％以上９０％以下が好ましく、７０％以上９０％以下がより好ましく、７５％以上８５％以下が最も好ましい。
ヘイズは、ＪＩＳ−Ｋ７１３６：２０００年、全光線透過率は、ＪＩＳ−Ｋ７３６１：１９９７年に準じて測定された値である。
本発明の一実施態様の合わせガラスは、既述の中間膜を有し、ヘイズ及び全光線透過率が上記の範囲にあることで、光透過性及び目隠し性に優れ、耐水性の高い合わせガラスとなる。<Laminated glass>
Laminated glass includes two glasses and at least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer disposed between the two glasses, And an intermediate film including the A film containing the ethylene-based polymer (excluding the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer). .
The laminated glass has a haze of 50% to 99.5% and a total light transmittance of 50% to 90%.
When the haze is less than 50%, the blinding property is inferior, and when it exceeds 99.5%, the light transmittance is inferior. The haze is preferably 60% or more and 99.5% or less, more preferably 80% or more and 99.5% or less, further preferably 85% or more and 99.5% or less, and more preferably 90% or more and 99.5% or less. 90% to 99% is most preferable.
When the total light transmittance is less than 50%, the light transmittance is inferior, and when it exceeds 90%, the blinding property is inferior. The total light transmittance is preferably 60% to 90%, more preferably 70% to 90%, and most preferably 75% to 85%.
The haze is a value measured according to JIS-K7136: 2000, and the total light transmittance is a value measured according to JIS-K7361: 1997.
The laminated glass of one embodiment of the present invention has the above-described intermediate film, and has a haze and total light transmittance in the above ranges, so that it is excellent in light transmission and blinding, and has high water resistance. It becomes.
合わせガラスの構成としては、例えば、シート状のガラス／中間膜（Ａ膜単膜）／シート状のガラスの構成が挙げられる。
また、中間膜は、最外層としてＢ膜を有していてもよく、合わせガラスの構成としては、例えば、シート状のガラス／中間膜（Ｂ膜／Ａ膜／Ｂ膜）／シート状のガラスの構成であってもよい。更に、これらの構成の中で、少なくとも１層に着色剤が配合されている構成なども挙げられる。As a structure of a laminated glass, the structure of sheet-like glass / intermediate film (A film single film) / sheet-like glass is mentioned, for example.
Further, the intermediate film may have a B film as the outermost layer, and the laminated glass may have, for example, a sheet-like glass / intermediate film (B film / A film / B film) / sheet-like glass. It may be configured as follows. Furthermore, among these configurations, a configuration in which a colorant is blended in at least one layer is also included.
シート状のガラスの材質は特に限定されず、ソーダライムガラスが好適に使用されるが、中でも高透過ガラス（いわゆる白板ガラス）が好ましく使用される。高透過ガラスは、鉄分の含有量の少ないソーダライムガラスであり、全光線透過率の高いガラスである。また、シート状のガラスとしては、表面にエンボス模様を施した型板ガラスも好適に使用される。また、シート状のガラスとしては、鉄分含有量の多いソーダライムガラス（いわゆる青板ガラス）、熱線反射ガラス、及び熱線吸収ガラスなども好ましく使用できる。
シート状のガラス（又はガラス板）の厚みは特に制限がないが、通常は４ｍｍ以下、好ましくは２．５ｍｍ以下である。シート状のガラスの厚みの下限は制限が無いものの、通常は０．１ｍｍ以上、好ましくは０．５ｍｍ以上である。The material of the sheet-like glass is not particularly limited, and soda lime glass is preferably used. Among them, highly transmissive glass (so-called white plate glass) is preferably used. High transmission glass is soda-lime glass with a low iron content, and is a glass with high total light transmittance. Moreover, as the sheet-like glass, a template glass having an embossed pattern on the surface is also preferably used. Further, as the sheet-like glass, soda lime glass (so-called blue plate glass) having a high iron content, heat ray reflective glass, heat ray absorbing glass and the like can be preferably used.
The thickness of the sheet-like glass (or glass plate) is not particularly limited, but is usually 4 mm or less, preferably 2.5 mm or less. The lower limit of the thickness of the sheet-like glass is not limited, but is usually 0.1 mm or more, preferably 0.5 mm or more.
合わせガラスの製造は、例えば、２枚のシート状のガラスの間に前記合わせガラス用中間膜（Ａ膜単膜又は多層を有する中間膜）を入れ、加熱及び加圧下で熱圧着することで行うことができる。加熱温度は、例えば、１００℃〜２５０℃程度が好ましく、圧力は、例えば、０．１ｋｇ／ｃｍ２〜３０ｋｇ/ｃｍ２程度が好ましい。The production of laminated glass is performed, for example, by placing the interlayer film for laminated glass (an A film having a single film or a multilayer film) between two sheets of glass, and thermocompression bonding under heating and pressure. be able to. The heating temperature is, for example, preferably about 100 ° C. to 250 DEG ° C., the pressure is, for example, 0.1kg / cm 2 ~30kg / cm 2 is preferably about.
以下、本発明の一実施態様を実施例により更に具体的に説明するが、本発明の一実施態様はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」は質量基準である。 Hereinafter, one embodiment of the present invention will be described more specifically with reference to examples. However, one embodiment of the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.
下記の実施例及び比較例に用いた材料、各層の配合、基材、及び評価方法は、次の通りである。 The materials used in the following Examples and Comparative Examples, the composition of each layer, the base material, and the evaluation method are as follows.
−（１）樹脂−
以下の樹脂原料を用意した。
１．エチレン・酢酸ビニル共重合体（ＥＶＡ）
酢酸ビニルに由来する構成単位含有量＝４１質量％
エチレンに由来する構成単位含有量＝５９質量％
２．エチレン・メタクリル酸共重合体（Ｅ−ＭＡＡ）
メタクリル酸に由来する構成単位含有量＝４質量％
エチレンに由来する構成単位含有量＝９６質量％
３．エチレン・メタクリル酸共重合体のＺｎアイオノマー
メタクリル酸に由来する構成単位含有量＝９質量％
エチレンに由来する構成単位含有量＝９１質量％
中和イオン＝Ｚｎイオン
中和度＝１８％
４．ポリエチレン（ＨＤＰＥ）
(株)プライムポリマー社製 ハイゼックス７０００Ｆ
ＭＦＲ（１９０℃、２１６０ｇ荷重）＝０．０４ｇ／１０分
５．エチレン・アクリル酸メチル共重合体（ＥＭＡ）
アクリル酸メチルに由来する構成単位含有量＝２０質量％
エチレンに由来する構成単位含有量＝８０質量％
ＭＦＲ（１９０℃、２１６０ｇ荷重）＝８ｇ／１０分
６．エチレン・アクリル酸エチル共重合体（ＥＥＡ）
アクリル酸メチルに由来する構成単位含有量＝１５質量％
エチレンに由来する構成単位含有量＝８５質量％
ＭＦＲ（１９０℃、２１６０ｇ荷重）＝６ｇ／１０分-(1) Resin-
The following resin raw materials were prepared.
1. Ethylene / vinyl acetate copolymer (EVA)
Constituent unit content derived from vinyl acetate = 41% by mass
Content of structural unit derived from ethylene = 59% by mass
2. Ethylene / methacrylic acid copolymer (E-MAA)
Constituent unit content derived from methacrylic acid = 4% by mass
Content of structural unit derived from ethylene = 96% by mass
3. Zn ionomer of ethylene / methacrylic acid copolymer Content of structural unit derived from methacrylic acid = 9% by mass
Content of structural unit derived from ethylene = 91% by mass
Neutralization ion = Zn ion Degree of neutralization = 18%
4). Polyethylene (HDPE)
Hi-Zex 7000F manufactured by Prime Polymer Co., Ltd.
4. MFR (190 ° C., 2160 g load) = 0.04 g / 10 min Ethylene / methyl acrylate copolymer (EMA)
Constituent unit content derived from methyl acrylate = 20% by mass
Content of structural unit derived from ethylene = 80 mass%
MFR (190 ° C., 2160 g load) = 8 g / 10 minutes Ethylene / ethyl acrylate copolymer (EEA)
Constituent unit content derived from methyl acrylate = 15% by mass
Content of structural unit derived from ethylene = 85% by mass
MFR (190 ° C., 2160 g load) = 6 g / 10 min
−（２）基材−
以下の基材を用意した。
厚み３．２ｍｍの青板強化ガラス（旭硝子（株）製）
−（３）Ｂ膜−
Ｂ膜には、以下の樹脂膜を用いた。
上記のアイオノマー８０部と、上記のＥ−ＭＡＡ２０部と、シランカップリング剤（Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン：信越化学工業（株）製の「ＫＢＭ６０２」）０．２部と、を混合し、Ｂ膜形成用組成物を作製し、単層Ｔ−ダイ成形機により、樹脂温度１６０℃の条件にて、膜厚７５μｍとなるように樹脂膜を製膜した。-(2) Base material-
The following base materials were prepared.
3.2mm thick blue plate tempered glass (Asahi Glass Co., Ltd.)
-(3) B film-
The following resin films were used for the B film.
80 parts of the above ionomer, 20 parts of the above E-MAA, and a silane coupling agent (N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane: “KBM602” manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts are mixed to prepare a composition for forming a B film, and a resin film is formed by a single layer T-die molding machine so as to have a film thickness of 75 μm at a resin temperature of 160 ° C. .
［実施例１］
上記のＥＶＡを２８部と、上記のＥ−ＭＡＡを７２部と、を混合し、いずれも、ダイ幅４０ｍｍのダイスを装着した４０ｍｍφコートハンガーダイ異形成形機（ナカタニ機械（株）製）を用いて、厚み２５０μｍの単層シート（Ａ膜）を作製した。
次に厚み３．２ｍｍの青板強化ガラス（７５ｍｍ×１２０ｍｍ）、上記のＢ膜、上記で得られた厚み２５０μｍの単層シート（Ａ膜）、上記のＢ膜、および厚み３．２ｍｍの青板強化ガラス（７５ｍｍ×１２０ｍｍ）をこの順に積層し、積層体を真空加熱貼合器（ＬＭ−５０ｘ５０Ｓ、ＮＰＣ社製の２重真空槽貼り合せ機）を用い、１５０℃、８分間の条件で貼り合わせ、青板強化ガラス／中間膜（Ｂ膜／Ａ膜／Ｂ膜）／青板強化ガラスからなる構成の合わせガラス試料を作製した。[Example 1]
28 parts of the above EVA and 72 parts of the above E-MAA were mixed, both using a 40 mmφ coat hanger die profile machine (manufactured by Nakatani Machinery Co., Ltd.) equipped with a die having a die width of 40 mm. Thus, a single layer sheet (A film) having a thickness of 250 μm was produced.
Next, a 3.2 mm thick blue sheet tempered glass (75 mm × 120 mm), the B film, the single layer sheet (A film) 250 μm thick obtained above, the B film, and a blue film with a thickness of 3.2 mm Sheet tempered glass (75 mm x 120 mm) is laminated in this order, and the laminate is laminated at 150 ° C for 8 minutes using a vacuum heating laminator (LM-50x50S, double vacuum tank laminator manufactured by NPC). The laminated glass sample of the structure which consists of bonding and a blue plate tempered glass / intermediate film (B film / A film / B film) / blue plate tempered glass was produced.
＜評価＞
得られた合わせガラス試料を用い、下記の各種評価を実施した。評価結果を下記表１に示す。<Evaluation>
The following various evaluation was implemented using the obtained laminated glass sample. The evaluation results are shown in Table 1 below.
（ヘイズ及び全光線透過率）
合わせガラス試料を用い、ヘイズメーター（スガ試験機社製）にて、ＪＩＳ−Ｋ７３６１に準じて全光線透過率（％）を、ＪＩＳ−Ｋ７１３６に準じてヘイズ（％）を、それぞれ測定した。(Haze and total light transmittance)
Using the laminated glass sample, the total light transmittance (%) was measured according to JIS-K7361 and the haze (%) was measured according to JIS-K7136 with a haze meter (manufactured by Suga Test Instruments Co., Ltd.).
（耐水性）
合わせガラス試料を１００℃の沸騰水中で２時間煮沸し、煮沸後の試料について、外観を目視で観察、並びにヘイズ及び全光線透過率を測定し、以下の基準に従い耐水性を評価した。なお、試料の変色の度合いが大きいほど、耐水性が悪いと評価した。(water resistant)
The laminated glass sample was boiled in boiling water at 100 ° C. for 2 hours, and the appearance of the sample after boiling was visually observed, the haze and the total light transmittance were measured, and the water resistance was evaluated according to the following criteria. In addition, it evaluated that water resistance was so bad that the degree of discoloration of a sample was large.
−評価基準−
Ａ：外観変化がなく、ヘイズ及び全光線透過率の変化率がいずれも３％未満である。
Ｂ：外観変化があり、ヘイズ及び全光線透過率の変化率のいずれか一方が３％以上である。-Evaluation criteria-
A: There is no change in appearance, and both the haze and the change rate of the total light transmittance are less than 3%.
B: There is a change in appearance, and either one of the change rate of haze and total light transmittance is 3% or more.
［実施例２〜実施例４］
実施例１において、Ａ膜の樹脂の種類および配合比率を下記表１に示すように変更した以外は、実施例１と同様にして各実施例の合わせガラス試料を作製した。
また、各実施例の合わせガラス試料についても、実施例１と同様、各種評価を実施した。評価結果を表１に示す。[Examples 2 to 4]
In Example 1, laminated glass samples of each example were produced in the same manner as in Example 1 except that the type of resin of the A film and the blending ratio thereof were changed as shown in Table 1 below.
Further, various evaluations were performed on the laminated glass samples of each Example as in Example 1. The evaluation results are shown in Table 1.
［比較例１］
実施例１における中間膜の樹脂を上記のＥＶＡ１００部に変更した以外は実施例１と同様にして合わせガラス試料を作製した。また、比較例１の合わせガラス試料についても、実施例１と同様に各種評価を実施した。評価結果を表１に示す。[Comparative Example 1]
A laminated glass sample was produced in the same manner as in Example 1 except that the resin of the interlayer film in Example 1 was changed to 100 parts of the above EVA. Further, the laminated glass sample of Comparative Example 1 was subjected to various evaluations as in Example 1. The evaluation results are shown in Table 1.
表１より、実施例１〜実施例４は、目隠し性に優れ、耐水性が高いことがわかる。
比較例１は、ヘイズが低く、目隠し性に劣ることがわかる。また、比較例１は、図１に示すように、白化しており耐水性に劣ることがわかる。From Table 1, it can be seen that Examples 1 to 4 are excellent in blinding and have high water resistance.
It can be seen that Comparative Example 1 has low haze and poor blinding. Moreover, it turns out that the comparative example 1 is white and inferior to water resistance, as shown in FIG.
２０１４年１０月１５日に出願された日本国特許出願２０１４−２１０７３８号の開示はその全体が参照により本明細書に取り込まれる。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。The disclosure of Japanese Patent Application No. 2014-210738 filed on Oct. 15, 2014 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.
Claims (7)
前記２枚のガラス間に配置されたエチレン・不飽和カルボン酸エステル共重合体及びエチレン・ビニルエステル共重合体から選ばれる少なくとも１種の共重合体とエチレン系重合体（ただし、前記エチレン・不飽和カルボン酸エステル共重合体及び前記エチレン・ビニルエステル共重合体を除く）とを含有するＡ膜を含む中間膜を有し、
ヘイズが５０％以上９９．５％以下であり、全光線透過率が５０％以上９０％以下である合わせガラス。Two glasses,
At least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer disposed between the two glasses and an ethylene polymer (provided that the ethylene An intermediate film including an A film containing a saturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer),
Laminated glass having a haze of 50% to 99.5% and a total light transmittance of 50% to 90%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014210738 | 2014-10-15 | ||
| JP2014210738 | 2014-10-15 | ||
| PCT/JP2015/079080 WO2016060176A1 (en) | 2014-10-15 | 2015-10-14 | Laminated glass and interlayer film for laminated glass |
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| JPWO2016060176A1 true JPWO2016060176A1 (en) | 2017-07-27 |
| JP6635933B2 JP6635933B2 (en) | 2020-01-29 |
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| JP (1) | JP6635933B2 (en) |
| KR (1) | KR101944448B1 (en) |
| CN (1) | CN106795048B (en) |
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| WO (1) | WO2016060176A1 (en) |
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| CN109641794B (en) * | 2016-08-30 | 2022-10-14 | 三井-陶氏聚合化学株式会社 | Resin composition and use thereof |
| JP7133084B2 (en) * | 2019-03-20 | 2022-09-07 | 三井・ダウポリケミカル株式会社 | Resin composition for laminated glass interlayer film, laminated glass interlayer film, and laminated glass |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57153064A (en) * | 1981-03-18 | 1982-09-21 | Sumitomo Chem Co Ltd | Adhesive resin composition |
| JPS6114243A (en) * | 1984-06-29 | 1986-01-22 | Yokohama Rubber Co Ltd:The | Resin composition for interlayer of laminated glass |
| JPH069932A (en) * | 1992-06-25 | 1994-01-18 | Tosoh Corp | Adhesive composition |
| JPH08295541A (en) * | 1995-04-21 | 1996-11-12 | Du Pont Mitsui Polychem Co Ltd | Intermediate film for laminated glass |
| JP2009298046A (en) * | 2008-06-13 | 2009-12-24 | Du Pont Mitsui Polychem Co Ltd | Multilayer sheet |
| JP2014058409A (en) * | 2012-09-14 | 2014-04-03 | Du Pont Mitsui Polychem Co Ltd | Intermediate film for laminated glass and laminated glass |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG42380A1 (en) * | 1995-06-08 | 1997-08-15 | Sekisui Chemical Co Ltd | An interlayer film and laminated glass using the same |
| BRPI0606797B8 (en) * | 2005-02-03 | 2017-03-21 | Sekisui Chemical Co Ltd | interlayer for laminated glass and laminated glass |
| CN102905896B (en) * | 2010-05-13 | 2017-02-08 | 三井-杜邦聚合化学株式会社 | Multilayer material, sealing material for solar cell, interlayer for safety (laminated) glass, solar cell module, and safety (laminated) glass |
| JP6073590B2 (en) * | 2012-01-27 | 2017-02-01 | 株式会社ブリヂストン | LAMINATE FORMING SHEET MANUFACTURING COMPOSITION, ITS MANUFACTURING METHOD, AND LAMINATE FORMING SHEET |
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- 2015-10-14 WO PCT/JP2015/079080 patent/WO2016060176A1/en active Application Filing
- 2015-10-14 KR KR1020177012444A patent/KR101944448B1/en active IP Right Grant
- 2015-10-14 JP JP2016554111A patent/JP6635933B2/en active Active
- 2015-10-14 CN CN201580055389.2A patent/CN106795048B/en active Active
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57153064A (en) * | 1981-03-18 | 1982-09-21 | Sumitomo Chem Co Ltd | Adhesive resin composition |
| JPS6114243A (en) * | 1984-06-29 | 1986-01-22 | Yokohama Rubber Co Ltd:The | Resin composition for interlayer of laminated glass |
| JPH069932A (en) * | 1992-06-25 | 1994-01-18 | Tosoh Corp | Adhesive composition |
| JPH08295541A (en) * | 1995-04-21 | 1996-11-12 | Du Pont Mitsui Polychem Co Ltd | Intermediate film for laminated glass |
| JP2009298046A (en) * | 2008-06-13 | 2009-12-24 | Du Pont Mitsui Polychem Co Ltd | Multilayer sheet |
| JP2014058409A (en) * | 2012-09-14 | 2014-04-03 | Du Pont Mitsui Polychem Co Ltd | Intermediate film for laminated glass and laminated glass |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106795048B (en) | 2019-12-06 |
| KR101944448B1 (en) | 2019-01-31 |
| WO2016060176A1 (en) | 2016-04-21 |
| TWI613169B (en) | 2018-02-01 |
| CN106795048A (en) | 2017-05-31 |
| KR20170066598A (en) | 2017-06-14 |
| JP6635933B2 (en) | 2020-01-29 |
| TW201620854A (en) | 2016-06-16 |
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