WO2015147302A1 - 合わせガラス用中間膜及び合わせガラス - Google Patents
合わせガラス用中間膜及び合わせガラス Download PDFInfo
- Publication number
- WO2015147302A1 WO2015147302A1 PCT/JP2015/059781 JP2015059781W WO2015147302A1 WO 2015147302 A1 WO2015147302 A1 WO 2015147302A1 JP 2015059781 W JP2015059781 W JP 2015059781W WO 2015147302 A1 WO2015147302 A1 WO 2015147302A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- laminated glass
- interlayer film
- polyvinyl acetal
- acetal resin
- Prior art date
Links
- 239000005340 laminated glass Substances 0.000 title claims abstract description 222
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 94
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000011354 acetal resin Substances 0.000 claims abstract description 93
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 93
- 239000004014 plasticizer Substances 0.000 claims abstract description 61
- 239000004611 light stabiliser Substances 0.000 claims abstract description 41
- 150000001412 amines Chemical class 0.000 claims abstract description 40
- 230000009477 glass transition Effects 0.000 claims abstract description 29
- 125000003386 piperidinyl group Chemical group 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 235
- 239000011229 interlayer Substances 0.000 claims description 80
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 23
- 230000021736 acetylation Effects 0.000 claims description 22
- 238000006640 acetylation reaction Methods 0.000 claims description 22
- 230000003078 antioxidant effect Effects 0.000 claims description 22
- 125000004429 atom Chemical group 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 27
- 238000006359 acetalization reaction Methods 0.000 description 20
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 16
- -1 polyethylene terephthalate Polymers 0.000 description 16
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 238000009413 insulation Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 6
- FRQDZJMEHSJOPU-UHFFFAOYSA-N Triethylene glycol bis(2-ethylhexanoate) Chemical compound CCCCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CCCC FRQDZJMEHSJOPU-UHFFFAOYSA-N 0.000 description 6
- 125000004036 acetal group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000005357 flat glass Substances 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000011800 void material Substances 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002895 organic esters Chemical class 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 3
- JEYLQCXBYFQJRO-UHFFFAOYSA-N 2-[2-[2-(2-ethylbutanoyloxy)ethoxy]ethoxy]ethyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CC JEYLQCXBYFQJRO-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- YJGHMLJGPSVSLF-UHFFFAOYSA-N 2-[2-(2-octanoyloxyethoxy)ethoxy]ethyl octanoate Chemical compound CCCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCCC YJGHMLJGPSVSLF-UHFFFAOYSA-N 0.000 description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001278 adipic acid derivatives Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- DLZBUNUDESZERL-UHFFFAOYSA-N 1-o-heptyl 6-o-nonyl hexanedioate Chemical compound CCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCC DLZBUNUDESZERL-UHFFFAOYSA-N 0.000 description 1
- XCTNDJAFNBCVOM-UHFFFAOYSA-N 1h-imidazo[4,5-b]pyridin-2-ylmethanamine Chemical compound C1=CC=C2NC(CN)=NC2=N1 XCTNDJAFNBCVOM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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
- CKQNDABUGIXFCL-UHFFFAOYSA-N 2-(2-octanoyloxyethoxy)ethyl octanoate Chemical compound CCCCCCCC(=O)OCCOCCOC(=O)CCCCCCC CKQNDABUGIXFCL-UHFFFAOYSA-N 0.000 description 1
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 1
- GCDUWJFWXVRGSM-UHFFFAOYSA-N 2-[2-(2-heptanoyloxyethoxy)ethoxy]ethyl heptanoate Chemical compound CCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCC GCDUWJFWXVRGSM-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- SSKNCQWPZQCABD-UHFFFAOYSA-N 2-[2-[2-(2-heptanoyloxyethoxy)ethoxy]ethoxy]ethyl heptanoate Chemical compound CCCCCCC(=O)OCCOCCOCCOCCOC(=O)CCCCCC SSKNCQWPZQCABD-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- VWSWIUTWLQJWQH-UHFFFAOYSA-N 2-butyl-6-[(3-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CCCCC1=CC(C)=CC(CC=2C(=C(CCCC)C=C(C)C=2)O)=C1O VWSWIUTWLQJWQH-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- BUVFHTMULQDARE-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid ethene Chemical group C=C.C(C)(C)(C)C=1C=C(C=C(C1O)C)CCC(=O)O.C(C)(C)(C)C=1C=C(C=C(C1O)C)CCC(=O)O BUVFHTMULQDARE-UHFFFAOYSA-N 0.000 description 1
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- BJIUNQZHYLBUNL-UHFFFAOYSA-N 6-heptoxy-6-oxohexanoic acid Chemical compound CCCCCCCOC(=O)CCCCC(O)=O BJIUNQZHYLBUNL-UHFFFAOYSA-N 0.000 description 1
- OIUGWVWLEGLAGH-UHFFFAOYSA-N 6-nonoxy-6-oxohexanoic acid Chemical compound CCCCCCCCCOC(=O)CCCCC(O)=O OIUGWVWLEGLAGH-UHFFFAOYSA-N 0.000 description 1
- HUUJFOGLCYMPCS-UHFFFAOYSA-N C(C)(C)(C)C(CC(C(O[P])OC1=CC=CC=C1)CC)CCC(C)(C)C Chemical compound C(C)(C)(C)C(CC(C(O[P])OC1=CC=CC=C1)CC)CCC(C)(C)C HUUJFOGLCYMPCS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MOABYHZDQQELLG-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCC MOABYHZDQQELLG-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FSRKEDYWZHGEGG-UHFFFAOYSA-N [2-(8-methylnonyl)phenyl] dihydrogen phosphate Chemical compound CC(C)CCCCCCCC1=CC=CC=C1OP(O)(O)=O FSRKEDYWZHGEGG-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VYCDFODYRFOXDA-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-undecoxypiperidin-4-yl) carbonate Chemical compound C1C(C)(C)N(OCCCCCCCCCCC)C(C)(C)CC1OC(=O)OC1CC(C)(C)N(OCCCCCCCCCCC)C(C)(C)C1 VYCDFODYRFOXDA-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
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- C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/012—Additives improving oxygen scavenging properties
Definitions
- the present invention relates to an interlayer film for laminated glass used for laminated glass. Moreover, this invention relates to the laminated glass using the said intermediate film for laminated glasses.
- Laminated glass is superior in safety even if it is damaged by an external impact and the amount of glass fragments scattered is small. For this reason, the said laminated glass is widely used for a motor vehicle, a rail vehicle, an aircraft, a ship, a building, etc.
- the laminated glass is manufactured by sandwiching an interlayer film for laminated glass between a pair of glass plates.
- Patent Document 1 As an example of the interlayer film for laminated glass, Patent Document 1 listed below has a low yellowing tendency, a high transmittance for UV-A rays and visible light, and a low transmittance for UV-B rays.
- An interlayer film having a rate is disclosed.
- This interlayer film contains polyvinyl acetal, a plasticizer, and an oxanilide type compound that is a UV absorber.
- Patent Document 1 describes that the intermediate film may contain a HAS / HALS / NOR-HALS type non-aromatic light stabilizer.
- Patent Document 2 discloses an intermediate film having high ultraviolet blocking characteristics and capable of maintaining optical quality over a long period of time.
- This intermediate film includes a polymer layer.
- the polymer layer includes a tungsten oxide agent and at least one of a molecule having a benzotriazole group and a polyvalent metal salt.
- Patent Document 3 discloses an interlayer film that can enhance sound insulation in a high frequency range of a laminated glass over a wide temperature range.
- the intermediate film is laminated on the first surface of the first layer including the polyvinyl acetal resin and the plasticizer, and the second layer includes the polyvinyl acetal resin and the plasticizer.
- a third layer that is laminated on a second surface opposite to the first surface of the first layer and includes a polyvinyl acetal resin and a plasticizer.
- the hydroxyl group content of the polyvinyl acetal resin contained in the first layer is lower than the hydroxyl group content of the polyvinyl acetal resin contained in the second and third layers.
- the ratio of the thickness of the first layer to the total thickness of the second layer and the third layer is 0.14 or less.
- Patent Document 3 describes that a laminated glass capable of suppressing the occurrence of foaming and the growth of foam can be obtained.
- the yellow index (YI) value of the end portion of the laminated glass may increase.
- An object of the present invention is to provide an interlayer film for laminated glass that hardly causes voids at the end of the laminated glass and can suppress an increase in the YI value at the end of the laminated glass.
- a first layer containing a polyvinyl acetal resin and a plasticizer, a first layer side of the first layer, the polyvinyl acetal resin and a plasticizer are disposed.
- the second layer further includes a hindered amine light stabilizer in which an alkyl group or an alkoxy group is bonded to a nitrogen atom of the piperidine structure, and the glass transition temperature of the second layer is An interlayer film for laminated glass having a temperature of 32 ° C. or higher is provided.
- the interlayer film includes at least one first metal atom selected from the group consisting of an alkaline earth metal, zinc, and aluminum, and the interlayer A film
- membrane does not contain an alkali metal or contains, and content of the said 1st metal atom in the said intermediate film is 150 ppm or less.
- content of the said plasticizer contained in the said 1st layer with respect to 100 weight part of said polyvinyl acetal resins contained in the said 1st layer is said 1st. More than the content of the plasticizer contained in the second layer with respect to 100 parts by weight of the polyvinyl acetal resin contained in the second layer.
- the polyvinyl acetal resin contained in the first layer is obtained by acetalizing polyvinyl alcohol having an average degree of polymerization of 1500 or more.
- the degree of acetylation of the polyvinyl acetal resin contained in the first layer is 0.1 mol% or more and 25 mol% or less, and the first The hydroxyl group content of the polyvinyl acetal resin contained in this layer is 20 mol% or more and less than 30 mol%.
- the glass transition temperature of the first layer is 20 ° C. or lower.
- the first layer includes an antioxidant having a molecular weight of 250 or more and including a phenol skeleton.
- the hindered amine light stabilizer has a molecular weight of 1000 or less.
- the interlayer film for laminated glass is disposed on the second surface side opposite to the first surface of the first layer, And a third layer containing a polyvinyl acetal resin and a plasticizer.
- the glass transition temperature of the third layer is 32 ° C. or higher.
- the interlayer film for laminated glass is used to obtain a laminated glass for an automobile.
- the first laminated glass member, the second laminated glass member, and the interlayer film for laminated glass described above are provided, and the first laminated glass member and the second laminated glass are provided.
- the interlayer film for laminated glass according to the present invention is disposed on the first surface side of the first layer including the polyvinyl acetal resin and the plasticizer, and the polyvinyl acetal resin and the plasticizer.
- the second layer further includes a hindered amine light stabilizer in which an alkyl group or an alkoxy group is bonded to a nitrogen atom of the piperidine structure, and the second layer includes the second layer. Since the glass transition temperature of the layer is 32 ° C. or higher, it is difficult for voids to occur at the edge of the laminated glass using the interlayer film for laminated glass according to the present invention, and the increase in the YI value is suppressed at the edge of the laminated glass. be able to.
- the first layer includes a hindered amine light stabilizer in which an alkyl group or an alkoxy group is bonded to a nitrogen atom of a piperidine structure, so that a void is formed at the end of the laminated glass. And an increase in the YI value can be suppressed at the edge of the laminated glass. Furthermore, in the interlayer film for laminated glass according to the present invention, even if the glass transition temperature of the second layer is 32 ° C. or higher, it is difficult for voids to occur at the edge of the laminated glass, and the edge of the laminated glass The rise in the YI value can be suppressed.
- FIG. 1 is a partially cutaway cross-sectional view schematically showing an interlayer film for laminated glass according to an embodiment of the present invention.
- FIG. 2 is a partially cutaway cross-sectional view schematically showing an example of laminated glass using the interlayer film for laminated glass shown in FIG.
- FIG. 1 schematically shows a partially cutaway sectional view of an interlayer film for laminated glass according to an embodiment of the present invention.
- the intermediate film 1 is a multilayer intermediate film having a structure of two or more layers.
- the intermediate film 1 is used to obtain a laminated glass.
- the intermediate film 1 has a laminated structure of two or more layers.
- the intermediate film 1 is an intermediate film for laminated glass.
- the intermediate film 1 is opposite to the first layer 2, the second layer 3 disposed on the first surface 2 a side of the first layer 2, and the first surface 2 a of the first layer 2.
- a third layer 4 disposed on the second surface 2b side.
- the second layer 3 is laminated on the first surface 2 a of the first layer 2.
- the third layer 4 is laminated on the second surface 2 b of the first layer 2.
- the first layer 2 is an intermediate layer.
- the second layer 3 and the third layer 4 are, for example, protective layers, and are surface layers in the present embodiment.
- the first layer 2 is disposed between the second layer 3 and the third layer 4 and is sandwiched between them. Therefore, the intermediate film 1 has a multilayer structure in which the
- the surface 3a opposite to the first layer 2 side of the second layer 3 is preferably a surface on which laminated glass members are laminated.
- the surface 4a opposite to the first layer 2 side of the third layer 4 is preferably the surface on which the laminated glass member is laminated.
- the other layer include a layer containing a thermoplastic resin such as polyvinyl acetal resin, and a layer containing polyethylene terephthalate.
- the first layer 2 and the second layer 3 each contain a polyvinyl acetal resin and a plasticizer.
- the first layer 2 includes a hindered amine light stabilizer.
- the hindered amine light stabilizer has a piperidine structure.
- the hindered amine light stabilizer contained in the first layer 2 is a hindered amine light stabilizer in which an alkyl group or an alkoxy group is bonded to the nitrogen atom of the piperidine structure.
- the glass transition temperature of the second layer 3 is 32 ° C. or higher.
- the intermediate film 1 Since the intermediate film 1 has the above-described configuration, it is difficult for voids to be generated at the end portion of the laminated glass using the intermediate film 1, and an increase in the YI value can be suppressed at the end portion of the laminated glass.
- the intermediate film 1 even if light is irradiated on the laminated glass using the intermediate film 1 for a long period of time or the laminated glass is exposed to a high temperature for a long period of time, it is difficult to form a void at the end of the laminated glass. it can. Furthermore, even if the laminated glass using the intermediate film 1 is exposed to a high temperature for a long time, an increase in the YI value can be suppressed.
- gap is a recessed part of the intermediate film which the intermediate film lost toward the inner side in the edge part of a laminated glass. For example, the recess is formed by the intermediate film retracting inward.
- the first layer 2 includes a hindered amine light stabilizer in which an alkyl group or an alkoxy group is bonded to a nitrogen atom of a piperidine structure, thereby making it difficult to generate voids at the edge of the laminated glass.
- an increase in the YI value can be suppressed at the end of the laminated glass.
- the second layer 3 and the third layer 4 are laminated one by one on both surfaces of the first layer 2. It is only necessary that the second layer is disposed on the first surface side of the first layer. Even if the second layer is disposed on the first surface side of the first layer and the third layer is not disposed on the second surface side of the first layer. Good. However, the second layer is disposed on the first surface side of the first layer, and the third layer is disposed on the second surface side of the first layer. It is preferable. By disposing the third layer on the second surface side of the first layer, the handleability of the intermediate film and the penetration resistance of the laminated glass are further enhanced.
- the adhesiveness with respect to a laminated glass member etc. can be adjusted with the surface of the both sides of an intermediate film.
- the adhesiveness with respect to the laminated glass member of the outer surface of the said 2nd layer of an intermediate film can be adjusted.
- the third layer preferably contains a polyvinyl acetal resin, preferably contains a plasticizer, and contains a polyvinyl acetal resin and a plastic. It is preferable to contain an agent.
- the glass transition temperature of the third layer is 32 ° C. or more from the viewpoint of effectively preventing voids at the edge of the laminated glass and effectively suppressing the increase in the YI value at the edge of the laminated glass. Therefore, the glass transition temperature of both the second layer and the third layer is preferably 32 ° C. or higher.
- the intermediate film preferably includes the second layer as a surface layer in the intermediate film.
- the intermediate film preferably includes the third layer as a surface layer in the intermediate film.
- the glass transition temperature of the second layer is preferably 33 ° C. from the viewpoint of effectively preventing voids at the edge of the laminated glass and effectively suppressing the increase in the YI value at the edge of the laminated glass. As mentioned above, More preferably, it is 35 degreeC or more.
- the glass transition temperature of the third layer is preferably 32 ° C. from the viewpoint of effectively preventing voids at the edge of the laminated glass and effectively suppressing the increase in the YI value at the edge of the laminated glass. As mentioned above, More preferably, it is 33 degreeC or more, More preferably, it is 35 degreeC or more.
- the upper limit of the glass transition temperature of the second layer and the third layer is not particularly limited. From the viewpoint of further improving the sound insulation of the interlayer film, the glass transition temperature of the second layer and the third layer may be 60 ° C. or less.
- the first layer includes a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (1)).
- the second layer contains a polyvinyl acetal resin (hereinafter may be referred to as a polyvinyl acetal resin (2)).
- the third layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (3)).
- the polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be the same or different.
- the said polyvinyl acetal resin (1), the said polyvinyl acetal resin (2), and the said polyvinyl acetal resin (3) only 1 type may respectively be used and 2 or more types may be used together.
- the polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde.
- the polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate.
- the saponification degree of the polyvinyl alcohol is generally 70 to 99.9 mol%.
- the average degree of polymerization of the polyvinyl alcohol is preferably 200 or more, more preferably 500 or more, still more preferably 1500 or more, still more preferably 1600 or more, particularly preferably 2600 or more, most preferably 2700 or more, preferably 5000 or less, More preferably, it is 4000 or less, More preferably, it is 3500 or less.
- the average degree of polymerization is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced.
- the average degree of polymerization is not more than the above upper limit, the intermediate film can be easily molded.
- the average degree of polymerization of the polyvinyl alcohol is 1500 or more, it is possible to prevent the appearance of the laminated glass from being deteriorated due to poor degassing.
- the average degree of polymerization of the polyvinyl alcohol is determined by a method based on JIS K6726 “Testing method for polyvinyl alcohol”.
- the carbon number of the acetal group contained in the polyvinyl acetal resin is not particularly limited.
- the aldehyde used when manufacturing the said polyvinyl acetal resin is not specifically limited.
- the carbon number of the acetal group in the polyvinyl acetal resin is preferably 3 to 5, and more preferably 3 or 4. When the carbon number of the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the intermediate film is sufficiently low.
- the aldehyde is not particularly limited. In general, an aldehyde having 1 to 10 carbon atoms is preferably used as the aldehyde.
- Examples of the aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, Examples include n-nonyl aldehyde, n-decyl aldehyde, and benzaldehyde.
- propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable
- propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferable
- n-butyraldehyde is still more preferable.
- the said aldehyde only 1 type may be used and 2 or more types may be used together.
- the hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably at least 17 mol%, more preferably at least 20 mol%, still more preferably at least 22 mol%, preferably at most 30 mol%. Is less than 27 mol%, more preferably 25 mol% or less.
- the adhesive strength of the interlayer film is further increased.
- the hydroxyl group content of the polyvinyl acetal resin (1) is 20 mol% or more, the reaction efficiency is high and the productivity is excellent, and when it is less than 27 mol%, the sound insulation of the laminated glass is further enhanced.
- the hydroxyl group content is not more than the above upper limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.
- the content of each hydroxyl group in the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 25 mol% or more, more preferably 28 mol% or more, preferably 35 mol% or less, more preferably 32 mol. % Or less.
- the hydroxyl group content is at least the above lower limit, the adhesive strength of the interlayer film is further increased. Further, when the hydroxyl group content is not more than the above upper limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.
- the hydroxyl group content of the polyvinyl acetal resin is a value indicating the mole fraction obtained by dividing the amount of ethylene groups to which the hydroxyl group is bonded by the total amount of ethylene groups in the main chain, as a percentage.
- the amount of the ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring according to JIS K6726 “Testing method for polyvinyl alcohol”.
- the degree of acetylation (acetyl group amount) of the polyvinyl acetal resin (1) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 7 mol% or more, still more preferably 9 It is at least mol%, preferably at most 30 mol%, more preferably at most 25 mol%, still more preferably at most 15 mol%.
- the acetylation degree is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is increased.
- the acetylation degree is not more than the above upper limit, the moisture resistance of the interlayer film and the laminated glass is increased.
- the degree of acetylation of the polyvinyl acetal resin (1) is 0.1 mol% or more and 25 mol% or less, the penetration resistance of the laminated glass is further improved.
- Each degree of acetylation of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 0.01 mol% or more, more preferably 0.5 mol% or more, preferably 10 mol% or less, more preferably. Is 2 mol% or less.
- the acetylation degree is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is increased.
- the acetylation degree is not more than the above upper limit, the moisture resistance of the interlayer film and the laminated glass is increased.
- the degree of acetylation is obtained by subtracting the amount of ethylene groups to which acetal groups are bonded and the amount of ethylene groups to which hydroxyl groups are bonded from the total amount of ethylene groups of the main chain, It is a value indicating the mole fraction obtained by dividing by the percentage.
- the amount of ethylene group to which the acetal group is bonded can be measured, for example, according to JIS K6728 “Testing method for polyvinyl butyral”.
- the degree of acetalization of the polyvinyl acetal resin (1) is preferably 47 mol% or more, more preferably 60 mol% or more, preferably 80 mol% or less, more preferably It is 70 mol% or less.
- the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases.
- the degree of acetalization is less than or equal to the above upper limit, the reaction time required for producing a polyvinyl acetal resin is shortened.
- the degree of acetalization (degree of butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 55 mol% or more, more preferably 67 mol% or more, preferably Is 75 mol% or less, more preferably 71 mol% or less.
- degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases.
- the degree of acetalization is less than or equal to the above upper limit, the reaction time required for producing a polyvinyl acetal resin is shortened.
- the above-mentioned degree of acetalization is a value indicating the mole fraction obtained by dividing the amount of ethylene groups to which acetal groups are bonded by the total amount of ethylene groups in the main chain as a percentage.
- the degree of acetalization can be calculated by a method based on JIS K6728 “Testing method for polyvinyl butyral”.
- the hydroxyl group content (hydroxyl content), acetalization degree (butyralization degree), and acetylation degree are preferably calculated from results measured by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. However, measurement according to ASTM D1396-92 JIS K6728 may be used.
- the polyvinyl acetal resin is a polyvinyl butyral resin
- the hydroxyl group content (hydroxyl amount), the acetalization degree (butyralization degree), and the acetylation degree are determined in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. It can be calculated from the results measured by
- the polyvinyl acetal resin (1) has an acetylation degree (a) of 8 mol% or less and an acetalization degree (a) of 70 mol%.
- the polyvinyl acetal resin (A) as described above is preferable, or the polyvinyl acetal resin (B) having a degree of acetylation (b) exceeding 8 mol% is preferable.
- the polyvinyl acetal resin (1) may be the polyvinyl acetal resin (A) or the polyvinyl acetal resin (B).
- the degree of acetylation (a) of the polyvinyl acetal resin (A) is 8 mol% or less, preferably 7.5 mol% or less, more preferably 7 mol% or less, still more preferably 6.5 mol% or less, particularly preferably. It is 5 mol% or less, preferably 0.1 mol% or more, more preferably 0.5 mol% or more, still more preferably 0.8 mol% or more, and particularly preferably 1 mol% or more.
- the degree of acetylation (a) is not more than the above upper limit and not less than the above lower limit, the migration of the plasticizer can be easily controlled, and the sound insulation of the laminated glass is further enhanced.
- the degree of acetalization (a) of the polyvinyl acetal resin (A) is 70 mol% or more, preferably 70.5 mol% or more, more preferably 71 mol% or more, still more preferably 71.5 mol% or more, particularly preferably. It is 72 mol% or more, preferably 85 mol% or less, more preferably 83 mol% or less, still more preferably 81 mol% or less, and particularly preferably 79 mol% or less.
- the acetalization degree (a) is not less than the above lower limit, the sound insulating properties of the laminated glass are further enhanced.
- the reaction time required in order to manufacture polyvinyl acetal resin (A) as the said acetalization degree (a) is below the said upper limit can be shortened.
- the hydroxyl group content (a) of the polyvinyl acetal resin (A) is preferably 18 mol% or more, more preferably 19 mol% or more, still more preferably 20 mol% or more, particularly preferably 21 mol% or more, preferably 31.
- the mol% or less more preferably 30 mol% or less, still more preferably 29 mol% or less, and particularly preferably 28 mol% or less.
- the hydroxyl group content (a) is not less than the above lower limit, the adhesive strength of the first layer is further increased.
- the hydroxyl group content (a) is not more than the above upper limit, the sound insulation of the laminated glass is further enhanced.
- the degree of acetylation (b) of the polyvinyl acetal resin (B) exceeds 8 mol%, preferably 9 mol% or more, more preferably 9.5 mol% or more, still more preferably 10 mol% or more, particularly preferably. 10.5 mol% or more, preferably 30 mol% or less, more preferably 28 mol% or less, still more preferably 26 mol% or less, and particularly preferably 24 mol% or less.
- the acetylation degree (b) is not less than the above lower limit, the sound insulation of the laminated glass is further enhanced.
- the reaction time required in order to manufacture polyvinyl acetal resin (B) as the said acetylation degree (b) is below the said upper limit can be shortened.
- the degree of acetalization (b) of the polyvinyl acetal resin (B) is preferably 50 mol% or more, more preferably 53 mol% or more, still more preferably 55 mol% or more, particularly preferably 60 mol% or more, preferably 80 mol%. % Or less, more preferably 78 mol% or less, still more preferably 76 mol% or less, and particularly preferably 74 mol% or less.
- the acetalization degree (b) is not less than the above lower limit, the sound insulating properties of the laminated glass are further enhanced.
- the reaction time required in order to manufacture polyvinyl acetal resin (B) as the said acetalization degree (b) is below the said upper limit can be shortened.
- the content (b) of the hydroxyl group in the polyvinyl acetal resin (B) is preferably 18 mol% or more, more preferably 19 mol% or more, still more preferably 20 mol% or more, particularly preferably 21 mol% or more, preferably 31.
- the hydroxyl group content (b) is not less than the above lower limit, the adhesive strength of the first layer is further increased.
- the hydroxyl group content (b) is not more than the above upper limit, the sound insulating properties of the laminated glass are further enhanced.
- the polyvinyl acetal resin (A) and the polyvinyl acetal resin (B) are each preferably a polyvinyl butyral resin.
- the first layer includes a plasticizer (hereinafter sometimes referred to as a plasticizer (1)).
- the second layer includes a plasticizer (hereinafter sometimes referred to as a plasticizer (2)).
- the third layer preferably contains a plasticizer (hereinafter sometimes referred to as a plasticizer (3)).
- plasticizer examples include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphate plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. . Of these, organic ester plasticizers are preferred.
- the plasticizer is preferably a liquid plasticizer.
- Examples of the monobasic organic acid ester include glycol esters obtained by a reaction between glycol and a monobasic organic acid.
- Examples of the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol.
- Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid, and decylic acid.
- polybasic organic acid ester examples include ester compounds of a polybasic organic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms.
- polybasic organic acid examples include adipic acid, sebacic acid, and azelaic acid.
- organic ester plasticizer examples include triethylene glycol di-2-ethylpropanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, Triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl Hexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-eth
- organic phosphate plasticizer examples include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
- the plasticizer is preferably a diester plasticizer represented by the following formula (1).
- R1 and R2 each represent an organic group having 2 to 10 carbon atoms
- R3 represents an ethylene group, an isopropylene group or an n-propylene group
- p represents an integer of 3 to 10
- R1 and R2 in the above formula (1) are each preferably an organic group having 5 to 10 carbon atoms, and more preferably an organic group having 6 to 10 carbon atoms.
- the plasticizer preferably contains triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH) or triethylene glycol di-2-ethylpropanoate. More preferably, it contains triethylene glycol di-2-ethylhexanoate or triethylene glycol di-2-ethylbutyrate, and more preferably contains triethylene glycol di-2-ethylhexanoate.
- 3GO triethylene glycol di-2-ethylhexanoate
- GGH triethylene glycol di-2-ethylbutyrate
- triethylene glycol di-2-ethylpropanoate More preferably, it contains triethylene glycol di-2-ethylhexanoate or triethylene glycol di-2-ethylbutyrate, and more preferably contains triethylene glycol di-2-ethylhexanoate.
- the content of the plasticizer (1) relative to 100 parts by weight of the polyvinyl acetal resin (1) is preferably 40 parts by weight or more, more preferably 55 parts by weight or more. , Preferably 90 parts by weight or less, more preferably 85 parts by weight or less.
- content (1) is not less than the above lower limit, the flexibility of the intermediate film is increased, and the handling of the intermediate film is facilitated.
- content (1) is not more than the above upper limit, the transparency of the interlayer film is further enhanced.
- the content of (3) (hereinafter sometimes referred to as content (3)) is preferably 30 parts by weight or more, more preferably 35 parts by weight or more, preferably 44 parts by weight or less, more preferably 42 parts by weight. Less than parts by weight.
- content (2) and the content (3) are each equal to or higher than the lower limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.
- the content (2) and the content (3) are each not more than the above upper limit, the penetration resistance of the laminated glass is further enhanced.
- the content (1) is preferably larger than the content (2) from the viewpoint of making it more difficult to form voids at the edge of the laminated glass, and the content (1) is preferably the content (3). It is preferable that there are more.
- the absolute value of the difference between the content (1) and the content (2), and the content (1) and the content (3) is preferably 10 parts by weight or more, more preferably 20 parts by weight or more.
- the absolute value of the difference between the content (1) and the content (2) and the absolute value of the difference between the content (1) and the content (3) are each preferably 50 parts by weight or less. is there.
- the first layer includes a hindered amine light stabilizer.
- the hindered amine light stabilizer contained in the first layer may be described as a hindered amine light stabilizer in which an alkyl group or an alkoxy group is bonded to the nitrogen atom of the piperidine structure (hereinafter referred to as a hindered amine light stabilizer (X)).
- a hindered amine light stabilizer X
- Each of the second layer and the third layer may contain a hindered amine light stabilizer and may not contain a hindered amine light stabilizer.
- the hindered amine light stabilizer contained in the second layer and the third layer is an alkyl group or a nitrogen atom in the piperidine structure.
- a hindered amine light stabilizer (X) to which an alkoxy group is bonded is preferable.
- the said hindered amine light stabilizer (X) only 1 type may be used and 2 or more types may be used together.
- the hindered amine light stabilizer (X) is preferably a hindered amine light stabilizer in which an alkyl group is bonded to a nitrogen atom of a piperidine structure, and a hindered amine light stabilizer in which an alkoxy group is bonded to a nitrogen atom of the piperidine structure. It is also preferable.
- Examples of the hindered amine light stabilizer in which an alkyl group is bonded to the nitrogen atom of the piperidine structure include TINUVIN 765, TINUVIN 622SF, and ADK STAB LA-52.
- hindered amine light stabilizers in which an alkoxy group is bonded to the nitrogen atom of the piperidine structure include TINUVIN XT-850FF, TINUVIN XT-855FF, and Adekastab LA-81.
- the molecular weight of the hindered amine light stabilizer (X) is preferably 2000 or less, more Preferably it is 1000 or less, More preferably, it is 700 or less.
- the content of the hindered amine light stabilizer (X) in 100% by weight of the first layer is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, preferably 0.5% by weight or less. More preferably, it is 0.3% by weight or less.
- the content of the hindered amine light stabilizer (X) is not less than the above lower limit and not more than the above upper limit, voids are less likely to occur at the end of the laminated glass, and the YI value is more increased at the end of the laminated glass. It can be further suppressed.
- the first layer may contain a hindered amine light stabilizer other than the hindered amine light stabilizer (X).
- the content of the hindered amine light stabilizer other than the hindered amine light stabilizer (X) in the first layer is preferably as small as possible, and the first layer has a hindered amine light stabilizer other than the hindered amine light stabilizer (X). It is preferable not to contain an agent.
- the content of a hindered amine light stabilizer other than the hindered amine light stabilizer (X) in 100% by weight of the first layer is preferably 0.2% by weight or less, more preferably 0.1% by weight or less.
- Each of the first layer, the second layer, and the third layer preferably contains an antioxidant.
- an antioxidant As for the said antioxidant, only 1 type may be used and 2 or more types may be used together.
- antioxidants examples include an antioxidant containing a phenol skeleton, an antioxidant containing sulfur, and an antioxidant containing phosphorus.
- the antioxidant is preferably an antioxidant containing a phenol skeleton or an antioxidant containing phosphorus, and an antioxidant containing a phenol skeleton. More preferably, it is an agent.
- antioxidant containing the phenol skeleton examples include 2,6-di-t-butyl-p-cresol (BHT), butylated hydroxyanisole (BHA), and 2,6-di-t-butyl-4-ethylphenol.
- antioxidant containing phosphorus examples include tridecyl phosphite, tris (tridecyl) phosphite, triphenyl phosphite, trinonylphenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, and bis (decyl) pentaerythritol disulfide.
- Phosphite tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl ester phosphorous acid, tris (2,4-di- t-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, and the like.
- the molecular weight of the antioxidant is preferably 200 or more, more preferably 300 or more, still more preferably 500 or more, and preferably 1500 or less.
- the content of the antioxidant is preferably 0.1% by weight or more, preferably 2% by weight or less, more preferably 1.8% by weight or less.
- the content of the antioxidant is not less than the above lower limit and not more than the above upper limit, voids are less likely to occur at the end of the laminated glass, and the increase in the YI value can be further suppressed at the end of the laminated glass. it can.
- the intermediate film preferably contains at least one first metal atom selected from the group consisting of alkali metals, zinc, and aluminum.
- the intermediate film does not contain or contains an alkaline earth metal.
- the first layer is a surface layer or the like, it is preferable that the first metal atom and the alkaline earth metal are each contained in the first layer.
- Each of the first metal atom and the alkaline earth metal is preferably contained in the second layer.
- Each of the first metal atom and the alkaline earth metal is preferably contained in the third layer.
- Use of the first metal atom and the alkaline earth metal makes it easy to control the adhesion between the laminated glass member and the interlayer film or the adhesion between the layers in the interlayer film.
- Each of the first metal atom and the alkaline earth metal may be blended in the form of a metal salt (hereinafter sometimes referred to as a metal salt (M)).
- M metal salt
- the metal salt (M) preferably contains at least one metal selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.
- the intermediate film preferably contains at least one metal of K and Mg.
- the metal salt (M) is more preferably an alkali metal salt of an organic acid having 2 to 16 carbon atoms or an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms. More preferably, it is a carboxylic acid magnesium salt or a C 2-16 carboxylic acid potassium salt.
- magnesium salt of carboxylic acid having 2 to 16 carbon atoms and the potassium salt of carboxylic acid having 2 to 16 carbon atoms include, but are not limited to, for example, magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, 2-ethylbutanoic acid
- magnesium, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate and potassium 2-ethylhexanoate examples include magnesium, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate and potassium 2-ethylhexanoate.
- the intermediate film contains the first metal atom
- the metal atom content and the second metal atom content in the third layer are each preferably 5 ppm or more, more preferably 10 ppm or more, still more preferably 20 ppm or more, preferably 300 ppm or less, more preferably 250 ppm or less, more preferably 200 ppm or less, and particularly preferably 150 ppm or less.
- the adhesiveness between the laminated glass member and the intermediate film or the adhesiveness between the layers in the intermediate film can be controlled better, and the laminated glass The increase in the YI value can be further suppressed at the end portion.
- the intermediate film contains an alkali metal
- the alkali metal content in each is preferably 5 ppm or more, more preferably 10 ppm or more, further preferably 20 ppm or more, preferably 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less, particularly preferably 150 ppm or less.
- the content of the alkali metal is not less than the above lower limit and not more than the above upper limit, the adhesion between the laminated glass member and the interlayer film or the adhesion between each layer in the interlayer film can be controlled even better, and the end of the laminated glass In this case, the increase in the YI value is further suppressed.
- Each of the first layer, the second layer, and the third layer is an ultraviolet shielding agent, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture resistant agent, and a fluorescent whitening as necessary.
- Additives such as an agent and an infrared absorber may be included. As for these additives, only 1 type may be used and 2 or more types may be used together.
- the alkali titer value of the first layer is a positive value. It is preferable.
- the glass transition temperature of the first layer is preferably 20 ° C. or lower.
- the glass transition temperature of the first layer is preferably ⁇ 15 ° C. or higher.
- the thickness of the interlayer film for laminated glass according to the present invention is not particularly limited. From the viewpoint of practical use and from the viewpoint of sufficiently increasing the heat shielding property, the thickness of the intermediate film is preferably 0.1 mm or more, more preferably 0.25 mm or more, preferably 3 mm or less, more preferably 1.5 mm or less. is there. When the thickness of the intermediate film is not less than the above lower limit, the penetration resistance of the laminated glass is increased. When the thickness of the interlayer film is not more than the above upper limit, the transparency of the interlayer film is further improved.
- T is the thickness of the intermediate film.
- the thickness of the first layer is preferably 0.0625 T or more, more Preferably it is 0.1T or more, Preferably it is 0.375T or less, More preferably, it is 0.25T or less.
- the thicknesses of the second layer and the third layer are preferably Is 0.625T or more, more preferably 0.75T or more, preferably 0.9375T or less, more preferably 0.9T or less.
- the bleeding out of a plasticizer can be suppressed as each thickness of a said 2nd layer and a said 3rd layer is more than the said minimum and below the said upper limit.
- the intermediate film includes the second layer and the third layer.
- the total thickness of the second layer and the third layer is preferably 0.625 T or more, more preferably 0.75 T or more, preferably 0.9375 T or less, more preferably 0.9 T or less. It is.
- the bleed-out of a plasticizer can be suppressed as the total thickness of the second layer and the third layer is not less than the lower limit and not more than the upper limit.
- the same polyvinyl acetal resin is contained in the second layer and the third layer, and the second layer, the third layer, It is more preferable that the same polyvinyl acetal resin and the same plasticizer are included, and it is more preferable that the second layer and the third layer are formed of the same resin composition.
- FIG. 2 An example of the laminated glass using the intermediate film for laminated glasses which concerns on one Embodiment of this invention is typically shown with sectional drawing.
- the laminated glass 11 shown in FIG. 2 includes a first laminated glass member 21, a second laminated glass member 22, and the intermediate film 1.
- the intermediate film 1 is disposed between the first laminated glass member 21 and the second laminated glass member 22 and is sandwiched.
- a first laminated glass member 21 is laminated on the first surface 1 a of the intermediate film 1.
- a second laminated glass member 22 is laminated on a second surface 1 b opposite to the first surface 1 a of the intermediate film 1.
- a first laminated glass member 21 is laminated on the outer surface 3 a of the second layer 3 of the intermediate film 1.
- a second laminated glass member 22 is laminated on the outer surface 4 a of the third layer 4 of the intermediate film 1.
- the laminated glass which concerns on this invention is the 1st laminated glass member, the 2nd laminated glass member, and the intermediate
- the intermediate film is the intermediate film for laminated glass of the present invention.
- the laminated glass member examples include a glass plate and a PET (polyethylene terephthalate) film.
- Laminated glass includes not only laminated glass in which an intermediate film is sandwiched between two glass plates, but also laminated glass in which an intermediate film is sandwiched between a glass plate and a PET film or the like.
- the laminated glass is a laminate including a glass plate, and preferably at least one glass plate is used.
- the first laminated glass member and the second laminated glass member are respectively a glass plate or a PET (polyethylene terephthalate) film, and the intermediate film is the first laminated glass member and the second laminated glass member. It is preferable that at least one glass plate is included. It is particularly preferable that both the first laminated glass member and the second laminated glass member are glass plates.
- the glass plate examples include inorganic glass and organic glass.
- the inorganic glass examples include float plate glass, heat ray absorbing plate glass, heat ray reflecting plate glass, polished plate glass, mold plate glass, and wire-containing plate glass.
- the organic glass is a synthetic resin glass substituted for inorganic glass.
- examples of the organic glass include polycarbonate plates and poly (meth) acrylic resin plates.
- Examples of the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate.
- the thickness of the laminated glass member is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less.
- the thickness of the glass plate is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less.
- the thickness of the PET film is preferably 0.03 mm or more, and preferably 0.5 mm or less.
- the method for producing the laminated glass is not particularly limited.
- the intermediate film is sandwiched between the first laminated glass member and the second laminated glass member, passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure, and the first The air remaining between the laminated glass member and the intermediate film and between the second laminated glass member and the intermediate film is degassed. Thereafter, it is pre-bonded at about 70 to 110 ° C. to obtain a laminate.
- the laminate is put in an autoclave or pressed and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, a laminated glass can be obtained.
- the interlayer film and the laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like.
- the said intermediate film and the said laminated glass can be used besides these uses.
- the interlayer film and the laminated glass are preferably a vehicle or architectural interlayer film and a laminated glass, and more preferably a vehicle interlayer film and a laminated glass.
- the intermediate film and the laminated glass can be used for an automobile windshield, side glass, rear glass, roof glass, or the like.
- the interlayer film and the laminated glass are suitably used for automobiles.
- the interlayer film is used for obtaining laminated glass for automobiles.
- the degree of butyralization degree of acetalization
- the degree of acetylation degree of acetylation
- the content of hydroxyl groups were determined by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. It was measured.
- ASTM D1396-92 the same numerical value as the method based on JIS K6728 “Testing method for polyvinyl butyral” was shown.
- HALS hindered amine light stabilizer
- TINUVIN 765 (manufactured by BASF, NC (alkyl group) type, molecular weight 509)
- TINUVIN 622SF (manufactured by BASF, NC (alkyl group) type, molecular weight 1000 or more)
- ADK STAB LA-81 (manufactured by ADEKA, N-OR (alkoxy group) type, molecular weight 678)
- TINUVIN XT-855FF manufactured by BASF, N-OR (alkoxy group) type
- TINUVIN 770DF (manufactured by BASF, NH (hydrogen atom) type, molecular weight 481) Hostavin N24 (manufactured by Clariant Japan, NH (hydrogen atom) type, molecular weight 632) Chimassorb 944FDL (manufactured by BASF, NH (hydrogen atom) type, molecular weight 1000 or more)
- BHT (2,6-di-t-butyl-p-cresol, molecular weight 220)
- IRGANOX 1010 manufactured by BASF, antioxidant containing phenol skeleton, molecular weight 117
- IRGANOX 245 made by BASF, antioxidant containing phenol skeleton, molecular weight 587)
- ADK STAB AO-40 manufactured by ADEKA, antioxidant containing phenol skeleton, molecular weight 383
- composition X for forming the first layer Polyvinyl acetal resin (polyvinyl butyral (PVB) resin, polyvinyl alcohol (PVA) average polymerization degree 2300, hydroxyl group content 23.2 mol%, acetylation degree 12.5 mol%, acetalization degree 64.3 mol%) 100 parts by weight, 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, 0.2 parts by weight of TINUVIN 765 (manufactured by BASF, N-alkyl group type, molecular weight 509) , BHT (2,6-di-t-butyl-p-cresol, molecular weight 220) 0.2 part by weight was mixed to obtain a composition X for forming the first layer.
- PVB polyvinyl butyral
- PVA polyvinyl alcohol
- composition Y for forming the second layer and the third layer Polyvinyl acetal resin (polyvinyl butyral (PVB) resin, polyvinyl alcohol (PVA) average polymerization degree 1700, hydroxyl group content 34.5 mol%, acetylation degree 0.8 mol%, acetalization degree 64.8 mol%) 100 parts by weight, 31.5 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO), which is a plasticizer, and an amount in which the magnesium content in the intermediate film is 60 ppm are mixed.
- the composition Y for forming the layer and the third layer was obtained.
- Preparation of interlayer film By co-extruding the composition X for forming the first layer and the composition Y for forming the second layer and the third layer using a co-extruder, the second layer An intermediate film (thickness 800 ⁇ m) having a laminated structure of (thickness 350 ⁇ m) / first layer (thickness 100 ⁇ m) / third layer (thickness 350 ⁇ m) was produced.
- Laminated glass production The obtained interlayer film (multilayer) was cut into a length of 8 cm and a width of 8 cm. Next, an intermediate film was sandwiched between two clear glasses (length 8 cm ⁇ width 8 cm ⁇ thickness 2.5 mm), held at 90 ° C. for 30 minutes with a vacuum laminator, and vacuum pressed to obtain a laminate. In the laminated body, the intermediate film portion protruding from the glass was cut off to obtain a laminated glass.
- Examples 2 to 21 and Comparative Examples 1 to 5 In the same manner as in Example 1, except that the types of components contained in the first layer, the second layer, and the third layer and the content of the components were set as shown in Tables 1 to 3 below. A film and laminated glass were produced.
- the glass transition temperature Tg was measured by the following method.
- the obtained multilayer interlayer film was stored at a temperature of 23 ° C. and a humidity of 30% for 1 month, and then isolated by peeling off each layer (first layer, second layer and third layer), and press molding machine
- the measurement object press-molded with an average thickness of 0.35 mm was allowed to stand for 2 hours at 25 ° C. and a relative humidity of 30%, and viscoelasticity was measured using “ARES-G2” manufactured by TAINSTRUMENTS.
- a parallel plate having a diameter of 8 mm was used, and the measurement was performed under the condition of decreasing the temperature from 100 ° C. to ⁇ 10 ° C.
- the peak temperature of the loss tangent was defined as the glass transition temperature Tg (° C.). In any method, the same glass transition temperature Tg was obtained.
- ⁇ At the end of the laminated glass, there is no gap, or the gap remains within a distance of 1 mm or less inward in the direction perpendicular to the edge having the end.
- ⁇ Laminated glass In the end portion, the gap extends from the end portion to a distance exceeding 1 mm inward in the direction orthogonal to the end side having the end portion.
- the initial YI value at the edge of the laminated glass was measured.
- the laminated glass was heated at 100 ° C. for 4 weeks. After heating, the YI value after heating at the edge of the laminated glass was measured.
- region of Y value was made into the area
- the absolute value of the difference between the initial YI value and the YI value after heating was determined as ⁇ YI.
- the laminated glass is vibrated with a vibration generator for vibration testing (“Vibrator G21-005D” manufactured by KENKEN Co., Ltd.), and the vibration characteristics obtained therefrom are mechanical impedance measuring device (manufactured by RION Co., Ltd.).
- the vibration spectrum was analyzed with an FFT spectrum analyzer ("FFT analyzer HP3582A” manufactured by Yokogawa Hured Packard).
- the glass transition temperature of the second layer and the third layer is 32 ° C. or higher.
- an intermediate film was obtained by changing the glass transition temperature of the second layer and the third layer to be less than 32 ° C. by changing only the kind of the polyvinyl acetal resin.
- the laminated glass there is a tendency that voids are more likely to occur at the edge of the laminated glass than the laminated glass using the interlayer film of Examples 1 to 21, and the YI value is at the edge of the laminated glass. There was a tendency to rise.
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Abstract
Description
上記第1の層は、ポリビニルアセタール樹脂(以下、ポリビニルアセタール樹脂(1)と記載することがある)を含む。上記第2の層は、ポリビニルアセタール樹脂(以下、ポリビニルアセタール樹脂(2)と記載することがある)を含む。上記第3の層は、ポリビニルアセタール樹脂(以下、ポリビニルアセタール樹脂(3)と記載することがある)を含むことが好ましい。上記ポリビニルアセタール樹脂(1)と上記ポリビニルアセタール樹脂(2)と上記ポリビニルアセタール樹脂(3)とは、同一であってもよく、異なっていてもよい。上記ポリビニルアセタール樹脂(1)、上記ポリビニルアセタール樹脂(2)及び上記ポリビニルアセタール樹脂(3)はそれぞれ、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記第1の層は可塑剤(以下、可塑剤(1)と記載することがある)を含む。上記第2の層は可塑剤(以下、可塑剤(2)と記載することがある)を含む。上記第3の層は可塑剤(以下、可塑剤(3)と記載することがある)を含むことが好ましい。ポリビニルアセタール樹脂と可塑剤との併用により、ポリビニルアセタール樹脂と可塑剤とを含む層の合わせガラス部材又は他の層に対する接着力が適度に高くなる。上記可塑剤は特に限定されない。上記可塑剤(1)と上記可塑剤(2)と上記可塑剤(3)とは同一であってもよく、異なっていてもよい。上記可塑剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記第1の層は、ヒンダードアミン光安定剤を含む。上記第1の層に含まれるヒンダードアミン光安定剤は、ピペリジン構造の窒素原子にアルキル基又はアルコキシ基が結合しているヒンダードアミン光安定剤(以下、ヒンダードアミン光安定剤(X)と記載することがある)である。上記第2の層及び上記第3の層はそれぞれ、ヒンダードアミン光安定剤を含んでいてもよく、ヒンダードアミン光安定剤を含んでいなくてもよい。上記第2の層及び上記第3の層がヒンダードアミン光安定剤を含む場合に、上記第2の層及び上記第3の層に含まれるヒンダードアミン光安定剤は、ピペリジン構造の窒素原子にアルキル基又はアルコキシ基が結合しているヒンダードアミン光安定剤(X)であることが好ましい。上記ヒンダードアミン光安定剤(X)は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記第1の層、上記第2の層及び上記第3の層はそれぞれ酸化防止剤を含むことが好ましい。上記酸化防止剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記中間膜は、アルカリ金属、亜鉛及びアルミニウムからなる群から選択された少なくとも1種の第1の金属原子を含むことが好ましい。上記中間膜は、アルカリ土類金属を含まないか、又は含む。第1の層が表面層である場合等には、上記第1の金属原子及び上記アルカリ土類金属はそれぞれ、上記第1の層に含まれることが好ましい。上記第1の金属原子及び上記アルカリ土類金属はそれぞれ、上記第2の層に含まれることが好ましい。上記第1の金属原子及び上記アルカリ土類金属はそれぞれ、上記第3の層に含まれることが好ましい。上記第1の金属原子及び上記アルカリ土類金属の使用により、合わせガラス部材と中間膜との接着性又は中間膜における各層間の接着性を制御することが容易になる。上記第1の金属原子及び上記アルカリ土類金属はそれぞれ、金属塩(以下、金属塩(M)と記載することがある)の状態で配合されてもよい。
上記第1の層、上記第2の層及び上記第3の層はそれぞれ、必要に応じて紫外線遮蔽剤、難燃剤、帯電防止剤、顔料、染料、接着力調整剤、耐湿剤、蛍光増白剤及び赤外線吸収剤等の添加剤を含んでいてもよい。これらの添加剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
合わせガラスの端部において空隙をより一層生じ難くし、かつ合わせガラスの端部においてYI値の上昇をより一層抑える観点からは、上記第1の層のアルカリタイターの値が、正の値であることが好ましい。
図2に、本発明の一実施形態に係る合わせガラス用中間膜を用いた合わせガラスの一例を模式的に断面図で示す。
TINUVIN 622SF(BASF社製、N-C(アルキル基)型、分子量1000以上)
アデカスタブ LA-81(ADEKA社製、N-OR(アルコキシ基)型、分子量678)
TINUVIN XT-855FF(BASF社製、N-OR(アルコキシ基)型)
TINUVIN 770DF(BASF社製、N-H(水素原子)型、分子量481)
Hostavin N24(クラリアントジャパン社製、N-H(水素原子)型、分子量632)
Chimassorb 944FDL(BASF社製、N-H(水素原子)型、分子量1000以上)
IRGANOX 1010(BASF社製、フェノール骨格を含む酸化防止剤、分子量1178)
IRGANOX 245(BASF社製、フェノール骨格を含む酸化防止剤、分子量587)
アデカスタブ AO-40(ADEKA社製、フェノール骨格を含む酸化防止剤、分子量383)
第1の層を形成するための組成物Xの作製:
ポリビニルアセタール樹脂(ポリビニルブチラール(PVB)樹脂、ポリビニルアルコール(PVA)の平均重合度2300、水酸基の含有率23.2モル%、アセチル化度12.5モル%、アセタール化度64.3モル%)100重量部と、可塑剤であるトリエチレングリコールジ-2-エチルヘキサノエート(3GO)60重量部と、TINUVIN 765(BASF社製、N-アルキル基型、分子量509)0.2重量部と、BHT(2,6-ジ-t-ブチル-p-クレゾール、分子量220)0.2重量部とを混合し、第1の層を形成するための組成物Xを得た。
ポリビニルアセタール樹脂(ポリビニルブチラール(PVB)樹脂、ポリビニルアルコール(PVA)の平均重合度1700、水酸基の含有率34.5モル%、アセチル化度0.8モル%、アセタール化度64.8モル%)100重量部と、可塑剤であるトリエチレングリコールジ-2-エチルヘキサノエート(3GO)31.5重量部と、中間膜中でマグネシウムの含有量が60ppmとなる量とを混合し、第2の層及び第3の層を形成するための組成物Yを得た。なお、マグネシウム混合物(酢酸マグネシウム:2-エチル酪酸マグネシウム=50重量%:50重量%)を用いた。
第1の層を形成するための組成物Xと、第2の層及び第3の層を形成するための組成物Yとを、共押出機を用いて共押出しすることにより、第2の層(厚み350μm)/第1の層(厚み100μm)/第3の層(厚み350μm)の積層構造を有する中間膜(厚み800μm)を作製した。
得られた中間膜(多層)を、縦8cm×横8cmに切り出した。次に、2枚のクリアガラス(縦8cm×横8cm×厚み2.5mm)の間に中間膜を挟み込み、真空ラミネーターにて90℃で30分間保持し、真空プレスし、積層体を得た。積層体において、ガラスからはみ出た中間膜部分を切り落とし、合わせガラスを得た。
第1の層、第2の層及び第3の層に含まれる成分の種類及び成分の含有量を下記の表1~3に示すように設定したこと以外は実施例1と同様にして、中間膜及び合わせガラスを作製した。
(1)第1の層のガラス転移温度
実施例及び比較例における第1の層の各組成を有する混練物を用意した。得られた混練物をプレス成型機でプレス成型して、平均厚さが0.35mmの樹脂膜Aを得た。得られた樹脂膜Aを25℃及び相対湿度30%の条件で2時間放置した。2時間放置した後に、TAINSTRUMENTS社製の「ARES-G2」を用いて、粘弾性を測定した。治具として、直径8mmのパラレルプレートを用いた。3℃/分の降温速度で100℃から-10℃まで温度を低下させる条件、及び周波数1Hz及び歪1%の条件で測定を行った。得られた測定結果において、損失正接のピーク温度をガラス転移温度Tg(℃)とした。
実施例及び比較例における第2の層及び第3の層の各組成を有する混練物を用意した。得られた混練物をプレス成型機でプレス成型して、平均厚さが0.35mmの樹脂膜Aを得た。得られた樹脂膜Aを25℃及び相対湿度30%の条件で2時間放置した。2時間放置した後に、TAINSTRUMENTS社製の「ARES-G2」を用いて、粘弾性を測定した。治具として、直径8mmのパラレルプレートを用いた。3℃/分の降温速度で100℃から-10℃まで温度を低下させる条件、及び周波数1Hz及び歪1%の条件で測定を行った。得られた測定結果において、損失正接のピーク温度をガラス転移温度Tg(℃)とした。
紫外線照射装置(スガ試験機社製「HLG-2S」)を用いて、JIS R3205に準拠して、紫外線(石英ガラス水銀灯(750W))を、合わせガラスに2000時間照射した。試験後に、合わせガラスの端部を観察し、合わせガラスの端部における空隙の状態を評価した。空隙の状態を下記の基準で判定した。
○:合わせガラスの端部において、空隙がないか、又は、端部から該端部を有する端辺に直交する方向に内側に向かって1mm以下の距離までに空隙が留まっている
×:合わせガラスの端部において、端部から該端部を有する端辺に直交する方向に内側に向かって1mmを超える距離までに空隙が至っている
分光光度計(日立ハイテク社製「U-4100」)を用いて、JIS K7105に準拠して、得られた合わせガラスの透過法によるYI値(黄色度、イエローインデックス)を測定した。
○:ΔYI値が20以下
×:ΔYI値が20を超える
合わせガラスをダンピング試験用の振動発生機(振研社製「加振機G21-005D」)により加振し、そこから得られた振動特性を機械インピーダンス測定装置(リオン社製「XG-81」)にて増幅し、振動スペクトルをFFTスペクトラムアナライザー(横河ヒューレッドパッカード社製「FFTアナライザー HP3582A」)により解析した。
1a…第1の表面
1b…第2の表面
2…第1の層
2a…第1の表面
2b…第2の表面
3…第2の層
3a…外側の表面
4…第3の層
4a…外側の表面
11…合わせガラス
21…第1の合わせガラス部材
22…第2の合わせガラス部材
Claims (12)
- ポリビニルアセタール樹脂と可塑剤とを含む第1の層と、
前記第1の層の第1の表面側に配置されており、かつポリビニルアセタール樹脂と可塑剤とを含む第2の層とを備え、
前記第1の層が、ピペリジン構造の窒素原子にアルキル基又はアルコキシ基が結合しているヒンダードアミン光安定剤をさらに含み、
前記第2の層のガラス転移温度が32℃以上である、合わせガラス用中間膜。 - 中間膜が、アルカリ土類金属、亜鉛及びアルミニウムからなる群から選択された少なくとも1種の第1の金属原子を含み、
中間膜が、アルカリ金属を含まないか又は含み、
中間膜における前記第1の金属原子の含有量が150ppm以下である、請求項1に記載の合わせガラス用中間膜。 - 前記第1の層に含まれる前記ポリビニルアセタール樹脂100重量部に対する前記第1の層に含まれる前記可塑剤の含有量が、前記第2の層に含まれる前記ポリビニルアセタール樹脂100重量部に対する前記第2の層に含まれる前記可塑剤の含有量よりも多い、請求項1又は2記載の合わせガラス用中間膜。
- 前記第1の層に含まれる前記ポリビニルアセタール樹脂が、平均重合度が1500以上のポリビニルアルコールをアセタール化することにより得られる、請求項1~3のいずれか1項に記載の合わせガラス用中間膜。
- 前記第1の層に含まれる前記ポリビニルアセタール樹脂のアセチル化度が0.1モル%以上、25モル%以下であり、
前記第1の層に含まれる前記ポリビニルアセタール樹脂の水酸基の含有率が20モル%以上、30モル%未満である、請求項1~4のいずれか1項に記載の合わせガラス用中間膜。 - 前記第1の層のガラス転移温度が、20℃以下である、請求項1~5のいずれか1項に記載の合わせガラス用中間膜。
- 前記第1の層が、分子量が250以上であり、かつフェノール骨格を含む酸化防止剤を含む、請求項1~6のいずれか1項に記載の合わせガラス用中間膜。
- 前記ヒンダードアミン光安定剤の分子量が1000以下である、請求項1~7のいずれか1項に記載の合わせガラス用中間膜。
- 前記第1の層の前記第1の表面とは反対の第2の表面側に配置されており、かつポリビニルアセタール樹脂と可塑剤とを含む第3の層を備える、請求項1~8のいずれか1項に記載の合わせガラス用中間膜。
- 前記第3の層のガラス転移温度が32℃以上である、請求項9に記載の合わせガラス用中間膜。
- 自動車の合わせガラスを得るために用いられる、請求項1~10のいずれか1項に記載の合わせガラス用中間膜。
- 第1の合わせガラス部材と、
第2の合わせガラス部材と、
請求項1~11のいずれか1項に記載の合わせガラス用中間膜とを備え、
前記第1の合わせガラス部材と前記第2の合わせガラス部材との間に、前記合わせガラス用中間膜が配置されている、合わせガラス。
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KR1020167019912A KR102382229B1 (ko) | 2014-03-28 | 2015-03-27 | 접합 유리용 중간막 및 접합 유리 |
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