JP2008031013A - Intermediate film for laminated glass and laminated glass - Google Patents
Intermediate film for laminated glass and laminated glass Download PDFInfo
- Publication number
- JP2008031013A JP2008031013A JP2006207757A JP2006207757A JP2008031013A JP 2008031013 A JP2008031013 A JP 2008031013A JP 2006207757 A JP2006207757 A JP 2006207757A JP 2006207757 A JP2006207757 A JP 2006207757A JP 2008031013 A JP2008031013 A JP 2008031013A
- Authority
- JP
- Japan
- Prior art keywords
- laminated glass
- interlayer film
- calcium
- glass
- ppm
- 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 149
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 27
- 239000000853 adhesive Substances 0.000 claims abstract description 24
- 230000001070 adhesive effect Effects 0.000 claims abstract description 24
- 229910001422 barium ion Inorganic materials 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000011247 coating layer Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 239000004014 plasticizer Substances 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 239000011229 interlayer Substances 0.000 claims description 78
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000035515 penetration Effects 0.000 abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010410 layer Substances 0.000 abstract description 10
- 229910052709 silver Inorganic materials 0.000 abstract description 10
- 239000004332 silver Substances 0.000 abstract description 10
- 241000120551 Heliconiinae Species 0.000 description 22
- -1 For example Polymers 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 9
- 229910001425 magnesium ion Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000003607 modifier Substances 0.000 description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 7
- 239000011354 acetal resin Substances 0.000 description 7
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 7
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 6
- 239000001639 calcium acetate Substances 0.000 description 6
- 235000011092 calcium acetate Nutrition 0.000 description 6
- 229960005147 calcium acetate Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 241001206158 Blepsias cirrhosus Species 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 5
- 239000011654 magnesium acetate Substances 0.000 description 5
- 235000011285 magnesium acetate Nutrition 0.000 description 5
- 229940069446 magnesium acetate Drugs 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229960005069 calcium Drugs 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 229960002713 calcium chloride Drugs 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000004227 calcium gluconate Substances 0.000 description 2
- 235000013927 calcium gluconate Nutrition 0.000 description 2
- 229960004494 calcium gluconate Drugs 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229940095643 calcium hydroxide Drugs 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 2
- 239000001527 calcium lactate Substances 0.000 description 2
- 235000011086 calcium lactate Nutrition 0.000 description 2
- 229960002401 calcium lactate Drugs 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 150000002334 glycols Chemical class 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
- 238000004898 kneading Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- ALWXETURCOIGIZ-UHFFFAOYSA-N 1-nitropropylbenzene Chemical compound CCC([N+]([O-])=O)C1=CC=CC=C1 ALWXETURCOIGIZ-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
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 1
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 1
- WPMUZECMAFLDQO-UHFFFAOYSA-N 2-[2-(2-hexanoyloxyethoxy)ethoxy]ethyl hexanoate Chemical compound CCCCCC(=O)OCCOCCOCCOC(=O)CCCCC WPMUZECMAFLDQO-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
- 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 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
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- FAFOEOPGBVYEJH-UHFFFAOYSA-N C(CCC)(=O)O.C=C.C=C.C(COCCOCCO)O Chemical compound C(CCC)(=O)O.C=C.C=C.C(COCCOCCO)O FAFOEOPGBVYEJH-UHFFFAOYSA-N 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- LKZCRGABYQYUFX-UHFFFAOYSA-L barium(2+);dithiocyanate Chemical compound [Ba+2].[S-]C#N.[S-]C#N LKZCRGABYQYUFX-UHFFFAOYSA-L 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000011692 calcium ascorbate Substances 0.000 description 1
- 235000010376 calcium ascorbate Nutrition 0.000 description 1
- 229940047036 calcium ascorbate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229960003563 calcium carbonate Drugs 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 229960001714 calcium phosphate Drugs 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229940095672 calcium sulfate Drugs 0.000 description 1
- BLORRZQTHNGFTI-ZZMNMWMASA-L calcium-L-ascorbate Chemical compound [Ca+2].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] BLORRZQTHNGFTI-ZZMNMWMASA-L 0.000 description 1
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 description 1
- FYPVXEILSNEKOO-UHFFFAOYSA-L calcium;butanoate Chemical compound [Ca+2].CCCC([O-])=O.CCCC([O-])=O FYPVXEILSNEKOO-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HBYOLNPZXLHVQA-UHFFFAOYSA-J dicalcium dicarbonate Chemical compound [Ca+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HBYOLNPZXLHVQA-UHFFFAOYSA-J 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OJXOOFXUHZAXLO-UHFFFAOYSA-M magnesium;1-bromo-3-methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC(Br)=C1 OJXOOFXUHZAXLO-UHFFFAOYSA-M 0.000 description 1
- WWRYOAYBSQIWNU-UHFFFAOYSA-L magnesium;decanoate Chemical compound [Mg+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O WWRYOAYBSQIWNU-UHFFFAOYSA-L 0.000 description 1
- NYKBOLCRGNSBBC-UHFFFAOYSA-L magnesium;heptanoate Chemical compound [Mg+2].CCCCCCC([O-])=O.CCCCCCC([O-])=O NYKBOLCRGNSBBC-UHFFFAOYSA-L 0.000 description 1
- IBBBJHKSXOSPDK-UHFFFAOYSA-L magnesium;nonanoate Chemical compound [Mg+2].CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O IBBBJHKSXOSPDK-UHFFFAOYSA-L 0.000 description 1
- HPBJPFJVNDHMEG-UHFFFAOYSA-L magnesium;octanoate Chemical compound [Mg+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HPBJPFJVNDHMEG-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 125000005461 organic phosphorous group Chemical group 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- RWMKSKOZLCXHOK-UHFFFAOYSA-M potassium;butanoate Chemical compound [K+].CCCC([O-])=O RWMKSKOZLCXHOK-UHFFFAOYSA-M 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- OXFUXNFMHFCELM-UHFFFAOYSA-N tripropan-2-yl phosphate Chemical compound CC(C)OP(=O)(OC(C)C)OC(C)C OXFUXNFMHFCELM-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、耐貫通性に優れ、合わせガラス用中間膜とガラス板との界面に、銀層等の金属コーティング層が設けられた合わせガラスとしたときに、銀色の斑点の発生を抑制することができる合わせガラス用中間膜、及び、該合わせガラス用中間膜を用いてなる合わせガラスに関する。 The present invention has excellent penetration resistance, and suppresses the occurrence of silver spots when a laminated glass having a metal coating layer such as a silver layer provided at the interface between the interlayer film for laminated glass and the glass plate is used. The present invention relates to an interlayer film for laminated glass and a laminated glass formed using the interlayer film for laminated glass.
合わせガラスは、外部衝撃を受けて破損してもガラスの破片が飛散することが少なく安全であるため、自動車等の車両、航空機、建築物等の窓ガラス等として広く使用されている。合わせガラスとしては、少なくとも一対のガラス間に、例えば、可塑剤により可塑化されたポリビニルブチラール樹脂等のポリビニルアセタール樹脂からなる合わせガラス用中間膜を介在させ、一体化させたもの等が挙げられる。 Laminated glass is widely used as a window glass for vehicles such as automobiles, aircrafts, buildings, and the like because it is safe because it does not scatter glass fragments even if it is damaged by an external impact. Examples of the laminated glass include those obtained by integrating an interlayer film for laminated glass made of polyvinyl acetal resin such as polyvinyl butyral resin plasticized with a plasticizer between at least a pair of glasses.
このような合わせガラスのなかでも、合わせガラス用中間膜とガラス板との界面に金属コーティング層を有する合わせガラスは、熱線反射合わせガラスや低反射合わせガラスとして広く使用されている（特許文献１参照）。
ところが、このような合わせガラス用中間膜とガラス板との界面に金属コーティング層を有する合わせガラスには、金属コーティング層中に銀色の斑点が発生してしまうという問題があった。
Among such laminated glasses, laminated glass having a metal coating layer at the interface between an interlayer film for laminated glass and a glass plate is widely used as heat ray reflective laminated glass or low reflective laminated glass (see Patent Document 1). ).
However, such a laminated glass having a metal coating layer at the interface between the interlayer film for laminated glass and the glass plate has a problem that silver spots are generated in the metal coating layer.
合わせガラス用中間膜は、可塑剤により可塑化されたポリビニルブチラール樹脂に、接着力調整剤や紫外線吸収剤等の添加剤が添加された樹脂組成物から構成されている。このような樹脂組成物からなる合わせガラス用中間膜は、ポリビニルブチラール樹脂や添加剤等に由来する微量成分、例えば、接着力調整剤添加による、解離した残留イオン成分等が含まれている。
本発明者らは、鋭意検討の結果、従来の合わせガラス用中間膜に配合されている物質に由来する微量成分、特に残留イオン成分が銀色の斑点の発生に影響を与えていると仮定し、該イオン成分を配位子とし錯体を形成可能な物質を含有させることで、銀色の斑点の抑制作用を発現させることが可能であるかを検討した。その結果、合わせガラス用中間膜中に存在する残留イオン成分を捕捉可能な化合物を添加することで、銀色の斑点の発生が低減することを見出した。
The interlayer film for laminated glass is composed of a resin composition obtained by adding an additive such as an adhesion adjusting agent or an ultraviolet absorber to a polyvinyl butyral resin plasticized with a plasticizer. The interlayer film for laminated glass made of such a resin composition contains trace components derived from polyvinyl butyral resin, additives, and the like, for example, dissociated residual ion components due to the addition of an adhesion modifier.
As a result of intensive studies, the present inventors have assumed that trace components derived from substances blended in conventional interlayer films for laminated glass, particularly residual ion components, have affected the occurrence of silver spots, It was investigated whether the inhibitory action of silver spots could be expressed by including a substance capable of forming a complex with the ionic component as a ligand. As a result, it has been found that the occurrence of silver spots is reduced by adding a compound capable of capturing residual ion components present in the interlayer film for laminated glass.
具体的には、従来の合わせガラス用中間膜の接着力調整剤として、カリウムイオンや、マグネシウムイオン等が含有されているが、カリウムイオンやマグネシウムイオンでは、銀色の斑点を発生させると推定される該イオン成分を配位させることは困難であり、銀色の斑点の発生を抑制することはできなかった。
そこで、本発明者らは、カルシウムイオンやバリウムイオン等の錯体の中心金属となりうるイオン成分を添加することで、銀色の斑点の抑制効果が発現することを見出したが、長時間の抑制効果を発現するものではなかった。例えば、特許文献２には、カルシウムイオンが添加された合わせガラス用中間膜が開示されているが、ガラス板との界面に金属コーティング層を有する合わせガラスとして使用した場合、銀色の斑点の抑制効果が不充分であった。
Specifically, potassium ions, magnesium ions, and the like are included as conventional adhesive strength modifiers for laminated glass interlayers, but it is estimated that silver spots are generated with potassium ions and magnesium ions. It was difficult to coordinate the ionic component, and the occurrence of silver spots could not be suppressed.
Therefore, the present inventors have found that by adding an ionic component that can be a central metal of a complex such as calcium ion or barium ion, an inhibitory effect on silver spots appears, but the inhibitory effect for a long time is exhibited. It was not expressed. For example, Patent Document 2 discloses an interlayer film for laminated glass to which calcium ions have been added, but when used as a laminated glass having a metal coating layer at the interface with a glass plate, the effect of suppressing silver spots Was insufficient.
また、特許文献３には、合わせガラス用中間膜中のカルシウム含有量及びマグネシウム含有量が開示されているが、このようなマグネシウムとカルシウムが併用された合わせガラス用中間膜を適用した場合でも、銀色の斑点の抑制効果及びガラス板との接着力の異常亢進防止効果は満足するものではなかった。
本発明は、上記現状に鑑み、耐貫通性に優れ、合わせガラス用中間膜とガラス板との界面に、銀層等の金属コーティング層が設けられた合わせガラスとしたときに、銀色の斑点の発生を抑制することができる合わせガラス用中間膜、及び、該合わせガラス用中間膜を用いてなる合わせガラスを提供することを目的とする。 In view of the present situation, the present invention is excellent in penetration resistance, and when it is a laminated glass provided with a metal coating layer such as a silver layer at the interface between the interlayer film for laminated glass and the glass plate, It aims at providing the laminated glass which uses the intermediate film for laminated glasses which can suppress generation | occurrence | production, and this intermediate film for laminated glasses.
本発明は、マトリックス樹脂、可塑剤、接着力調整剤、並びに、カルシウムイオン及び／又はバリウムイオンを含有する合わせガラス用中間膜であって、前記接着力調整剤の含有量が２０〜６０ｐｐｍであり、前記カルシウムイオン及び／又はバリウムイオンの含有量が３０〜１２０ｐｐｍである合わせガラス用中間膜である。
以下に本発明を詳述する。
The present invention is a matrix resin, a plasticizer, an adhesive strength modifier, and an interlayer film for laminated glass containing calcium ions and / or barium ions, wherein the content of the adhesive strength modifier is 20 to 60 ppm. The interlayer film for laminated glass having a calcium ion and / or barium ion content of 30 to 120 ppm.
The present invention is described in detail below.
本発明者らは、鋭意検討したところ、接着力調整剤とカルシウムイオン及び／又はバリウムイオンを併用し、合わせガラス用中間膜中の含有量を所定の範囲に調整することで、耐貫通性に優れるとともに、銀色の斑点の発生を抑制できることを見出し、本発明を完成するに至った。 As a result of diligent study, the present inventors have used an adhesive force regulator and calcium ions and / or barium ions in combination, and by adjusting the content in the interlayer film for laminated glass to a predetermined range, the penetration resistance is improved. It has been found that it is excellent and that the occurrence of silver spots can be suppressed, and the present invention has been completed.
本発明の合わせガラス用中間膜は、マトリックス樹脂、可塑剤、接着力調整剤及びカルシウムイオン及び／又はバリウムイオンを含有する。
上記マトリックス樹脂としては特に限定されないが、例えば、ポリビニルアセタール樹脂等が好適である。上記ポリビニルアセタール樹脂としては、ポリビニルアルコールをアルデヒドによりアセタール化して得られるポリビニルアセタール樹脂であれば特に限定されるものではないが、ポリビニルブチラール樹脂が好適である。また、必要に応じて２種以上のポリビニルアセタール樹脂を併用してもよい。
上記ポリビニルアセタール樹脂のアセタール化度の好ましい下限は４０％、好ましい上限は８５％であり、より好ましい下限は６０％、より好ましい上限は７５％である。
The interlayer film for laminated glass of the present invention contains a matrix resin, a plasticizer, an adhesive force regulator and calcium ions and / or barium ions.
Although it does not specifically limit as said matrix resin, For example, polyvinyl acetal resin etc. are suitable. The polyvinyl acetal resin is not particularly limited as long as it is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde, but a polyvinyl butyral resin is preferable. Moreover, you may use together 2 or more types of polyvinyl acetal resin as needed.
The preferable lower limit of the degree of acetalization of the polyvinyl acetal resin is 40%, the preferable upper limit is 85%, the more preferable lower limit is 60%, and the more preferable upper limit is 75%.
上記ポリビニルアセタール樹脂は、ポリビニルアルコールをアルデヒドによりアセタール化することにより調製することができる。
上記原料となるポリビニルアルコールは、通常、ポリ酢酸ビニルを鹸化することにより得られ、鹸化度８０〜９９．８モル％のポリビニルアルコールが一般的に用いられる。
また、上記ポリビニルアルコールの重合度の好ましい下限は２００、好ましい上限は３０００である。２００未満であると、得られる合わせガラスの耐貫通性が低下することがあり、３０００を超えると、樹脂膜の成形性が悪くなり、しかも樹脂膜の剛性が大きくなり過ぎ、加工性が悪くなることがある。より好ましい下限は５００、より好ましい上限は２０００である。
The polyvinyl acetal resin can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
The polyvinyl alcohol as the raw material is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol having a saponification degree of 80 to 99.8 mol% is generally used.
Moreover, the preferable minimum of the polymerization degree of the said polyvinyl alcohol is 200, and a preferable upper limit is 3000. If it is less than 200, the penetration resistance of the resulting laminated glass may be lowered, and if it exceeds 3000, the moldability of the resin film is deteriorated, and the rigidity of the resin film is excessively increased, resulting in poor workability. Sometimes. A more preferred lower limit is 500, and a more preferred upper limit is 2000.
上記アルデヒドとしては特に限定されないが、一般には、炭素数が１〜１０のアルデヒドが好適に用いられる。上記炭素数が１〜１０のアルデヒドとしては特に限定されず、例えば、ｎ−ブチルアルデヒド、イソブチルアルデヒド、ｎ−バレルアルデヒド、２−エチルブチルアルデヒド、ｎ−ヘキシルアルデヒド、ｎ−オクチルアルデヒド、ｎ−ノニルアルデヒド、ｎ−デシルアルデヒド、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド等が挙げられる。なかでも、ｎ−ブチルアルデヒド、ｎ−ヘキシルアルデヒド、ｎ−バレルアルデヒドが好ましく、炭素数が４のｎ−ブチルアルデヒドがより好ましい。これらのアルデヒドは単独で用いてもよく、２種以上を併用してもよい。 Although it does not specifically limit as said aldehyde, Generally, a C1-C10 aldehyde is used suitably. The aldehyde having 1 to 10 carbon atoms is not particularly limited. For example, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonyl Examples include aldehyde, n-decyl aldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Of these, n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and n-butyraldehyde having 4 carbon atoms is more preferable. These aldehydes may be used alone or in combination of two or more.
上記可塑剤としては特に限定されず、例えば、ジヘキシルアジペート、トリエチレングリコール−ジ−２−エチルヘキサノエート、テトラエチレングリコール−ジ−２−エチルブチレート、テトラエチレングリコール−ジ−ヘプタノエート、トリエチレングリコール−ジ−ヘプタノエート等の液状可塑剤や、一塩基性有機酸エステル、多塩基性有機酸エステル等の有機系可塑剤；有機リン酸系、有機亜リン酸系等のリン酸系可塑剤等が挙げられる。 The plasticizer is not particularly limited, and examples thereof include dihexyl adipate, triethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylbutyrate, tetraethylene glycol-di-heptanoate, and triethylene. Liquid plasticizers such as glycol-di-heptanoate, organic plasticizers such as monobasic organic acid esters and polybasic organic acid esters; phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid Is mentioned.
上記一塩基性有機酸エステル系可塑剤としては特に限定されず、例えば、トリエチレングリコール、テトラエチレングリコール、トリプロピレングリコール等のグリコールと、酪酸、イソ酪酸、カプロン酸、２−エチル酪酸、ヘプチル酸、ｎ−オクチル酸、２−エチルヘキシル酸、ペラルゴン酸（ｎ−ノニル酸）、デシル酸等の一塩基性有機酸との反応によって得られたグリコール系エステルが挙げられる。なかでも、トリエチレングリコール−ジカプロン酸エステル、トリエチレングリコール−ジ−２−エチル酪酸エステル、トリエチレングリコール−ジ−ｎ−オクチル酸エステル、トリエチレングリコール−ジ−２−エチルヘキシル酸エステル等のトリエチレングリコール等が好適である。 The monobasic organic acid ester plasticizer is not particularly limited, and examples thereof include glycols such as triethylene glycol, tetraethylene glycol, and tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, and heptyl acid. , Glycol esters obtained by reaction with monobasic organic acids such as n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonyl acid), decyl acid and the like. Among them, triethylene glycol-dicaproate, triethylene glycol-di-2-ethylbutyrate, triethylene glycol-di-n-octylate, triethylene glycol-di-2-ethylhexyl ester, etc. Glycol and the like are preferred.
上記多塩基性有機酸エステル系可塑剤としては特に限定されず、例えば、アジピン酸、セバシン酸、アゼライン酸等の多塩基性有機酸と炭素数４〜８の直鎖状又は分枝状アルコールのエステル等が挙げられる。なかでも、ジブチルセバシン酸エステル、ジオクチルアゼライン酸エステル、ジブチルカルビトールアジピン酸エステル等が好適である。
上記有機リン酸系可塑剤としては特に限定されず、例えば、トリブトキシエチルホスフェート、イソデシルフェニルホスフェート、トリイソプロピルホスフェート等が挙げられる。
The polybasic organic acid ester plasticizer is not particularly limited. For example, a polybasic organic acid such as adipic acid, sebacic acid or azelaic acid and a linear or branched alcohol having 4 to 8 carbon atoms. Examples include esters. Of these, dibutyl sebacic acid ester, dioctyl azelaic acid ester, dibutyl carbitol adipic acid ester and the like are preferable.
The organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
上記可塑剤の含有量としては特に限定されないが、上記マトリックス樹脂１００重量部に対して、好ましい下限は２０重量部、好ましい上限は１００重量部である。２０重量部未満であると、本発明の合わせガラス用中間膜の耐貫通性が低下することがあり、１００重量部を超えると、可塑剤のブリードアウトが生じ、本発明の合わせガラス用中間膜の透明性や接着性が低下し、得られる合わせガラスの光学歪みが大きくなるおそれがある。より好ましい下限は３０重量部、より好ましい上限は６０重量部である。 Although it does not specifically limit as content of the said plasticizer, A preferable minimum is 20 weight part and a preferable upper limit is 100 weight part with respect to 100 weight part of said matrix resins. If the amount is less than 20 parts by weight, the penetration resistance of the interlayer film for laminated glass of the present invention may be lowered. If the amount exceeds 100 parts by weight, bleeding out of the plasticizer occurs, and the interlayer film for laminated glass of the present invention. There is a risk that the transparency and adhesiveness of the laminated glass will deteriorate and the optical distortion of the resulting laminated glass will increase. A more preferred lower limit is 30 parts by weight, and a more preferred upper limit is 60 parts by weight.
上記接着力調整剤としては、従来合わせガラス用中間膜の接着力調整剤として用いられているものが挙げられ特に限定されないが、なかでも、カリウムイオン、マグネシウムイオンが好適である。
本発明の合わせガラス用中間膜において、上記接着力調整剤は、本発明の合わせガラス用中間膜の製造過程において、上述したマトリックス樹脂や可塑剤からなる混合物中に、上記接着力調整剤の有機酸塩として添加される。具体的には、例えば、上記接着力調整剤がマグネシウムイオンの場合、酢酸マグネシウム、ヘプタン酸マグネシウム、オクタン酸マグネシウム、ノナン酸マグネシウム、デカン酸マグネシウム等の有機酸塩として添加される。また、上記接着力調整剤がカリウムイオンの場合、蟻酸カリウム、酢酸カリウム、酪酸カリウム、プロピオン酸カリウム、シュウ酸カリウム等の有機酸塩として添加される。
Examples of the adhesive force adjusting agent include those conventionally used as an adhesive force adjusting agent for interlayer films for laminated glass, and potassium ions and magnesium ions are preferred.
In the interlayer film for laminated glass of the present invention, the adhesive strength adjusting agent is an organic compound of the adhesive strength adjusting agent in the mixture of the matrix resin and the plasticizer described above in the production process of the interlayer film for laminated glass of the present invention. Added as the acid salt. Specifically, for example, when the adhesive strength modifier is magnesium ion, it is added as an organic acid salt such as magnesium acetate, magnesium heptanoate, magnesium octoate, magnesium nonanoate, magnesium decanoate and the like. Moreover, when the said adhesive force regulator is potassium ion, it adds as organic acid salts, such as potassium formate, potassium acetate, potassium butyrate, potassium propionate, potassium oxalate.
上記接着力調整剤の含有量としては、下限が２０ｐｐｍ、上限が６０ｐｐｍである。２０ｐｐｍ未満であると、本発明の合わせガラス用中間膜とガラス板との接着力が異常亢進し、合わせガラス全体として耐貫通性が低下する。６０ｐｐｍを超えると、本発明の合わせガラス用中間膜と、銀層等の金属コーティング層が設けられたガラス板とを用いて熱線反射合わせガラスや低反射合わせガラスを製造すると、銀色の斑点が発生することがある。好ましい下限は２３ｐｐｍ、好ましい上限は４０ｐｐｍである。 As content of the said adhesive force regulator, a minimum is 20 ppm and an upper limit is 60 ppm. If it is less than 20 ppm, the adhesive force between the interlayer film for laminated glass of the present invention and the glass plate is abnormally enhanced, and the penetration resistance of the laminated glass as a whole is lowered. When the content exceeds 60 ppm, silver spots occur when a heat ray reflective laminated glass or a low reflective laminated glass is produced using the interlayer film for laminated glass of the present invention and a glass plate provided with a metal coating layer such as a silver layer. There are things to do. A preferred lower limit is 23 ppm and a preferred upper limit is 40 ppm.
また、本発明の合わせガラス用中間膜は、上記接着力調整剤としてアセチルアセトンが添加されていてもよい。上述したマグネシウムイオン等と併用することで、上記マグネシウムイオン等の含有量を少なくすることができ、より好適に銀色の斑点の発生を抑制できる。 Moreover, the intermediate film for laminated glasses of this invention may add acetylacetone as the said adhesive force regulator. By using together with magnesium ion etc. which were mentioned above, content of the said magnesium ion etc. can be decreased and generation | occurrence | production of a silver spot can be suppressed more suitably.
本発明の合わせガラス用中間膜において、上記カルシウムイオン及び／又はバリウムイオンは、錯体の中心金属となる物質である。
上述したように、本発明の合わせガラス用中間膜は、ポリビニルブチラール樹脂や添加剤等に由来する微量成分、例えば、接着力調整剤添加による解離した残留イオン成分等が含まれている。製造後に残存する残留イオン成分を、上記カルシウムイオン及び／又はバリウムイオンが中心金属として配位結合し錯体を形成するため、本発明の合わせガラス用中間膜中の残留イオン成分を低減することができる。従って、本発明の合わせガラス用中間膜を、銀層等の金属コーティング層が設けられたガラス板間に挟持して製造した熱線反射合わせガラスや低反射合わせガラスは、上記金属コーティング層に銀色の斑点が発生することを抑制することができる。また、上記カルシウムイオン及び／又はバリウムイオンを添加することで、残留イオン成分の拡散を防止できるため、接着力調整剤の添加量を極微量にする必要もなく、本発明の合わせガラス用中間膜の耐貫通性も優れたものとなる。
In the interlayer film for laminated glass of the present invention, the calcium ion and / or barium ion is a substance that becomes the central metal of the complex.
As described above, the interlayer film for laminated glass of the present invention contains trace components derived from polyvinyl butyral resin, additives, and the like, for example, residual ion components dissociated by the addition of an adhesive strength modifier. The residual ion component remaining after the production is coordinated and formed as a complex with the calcium ion and / or barium ion as the central metal, so that the residual ion component in the interlayer film for laminated glass of the present invention can be reduced. . Therefore, the heat ray reflective laminated glass or the low reflective laminated glass produced by sandwiching the interlayer film for laminated glass of the present invention between the glass plates provided with a metal coating layer such as a silver layer has a silvery color on the metal coating layer. The occurrence of spots can be suppressed. In addition, since the diffusion of residual ion components can be prevented by adding the calcium ions and / or barium ions, it is not necessary to add an extremely small amount of the adhesive strength modifier, and the interlayer film for laminated glass of the present invention The penetration resistance is also excellent.
このようなカルシウムイオン及び／又はバリウムイオンの添加方法としては特に限定されず、本発明の合わせガラス用中間膜の製造時に、例えば、酢酸塩、硝酸塩又は塩化物等の有機酸塩又は無機酸塩として添加する方法が挙げられる。なかでも、上記カルシウムイオン及び／又はバリウムイオンは、銀色の斑点の発生に起因すると推定される残留イオン成分を効率良く配位させるために、酢酸塩や硝酸塩として添加されることが好ましい。 The method for adding such calcium ions and / or barium ions is not particularly limited. For example, an organic acid salt or inorganic acid salt such as acetate, nitrate, or chloride is used during the production of the interlayer film for laminated glass of the present invention. The method of adding as is mentioned. Especially, it is preferable that the said calcium ion and / or barium ion are added as acetate or nitrate in order to coordinate efficiently the residual ion component estimated to originate in generation | occurrence | production of a silver spot.
上記カルシウムイオンの有機酸塩又は無機酸塩としては、特に限定されないが、分解温度が低いものもあるので、なるべく高いものを選択することが好ましい。また、上記カルシウムイオンの添加量は少ないので着色の原因にはなり難いが、無色の物質であることがより好ましい。
具体的には、例えば、酢酸カルシウム、硝酸カルシウム、硫酸カルシウム、水酸化カルシウム、アスコルビン酸カルシウム 、ほう化カルシウム 、ギ酸カルシウム、酪酸カルシウム、チオシアン酸カルシウム、しゅう酸カルシウム、次亜塩素酸カルシウム、炭酸カルシウム、グルコン酸カルシウム、乳酸カルシウム、リン酸カルシウム、塩化カルシウム等が挙げられ、水溶液になる塩として、酢酸カルシウム、硝酸カルシウム、炭酸カルシウム、グルコン酸カルシウム、乳酸カルシウム、塩化カルシウム、水酸化カルシウムを選択することが好ましい。
Although it does not specifically limit as said organic acid salt or inorganic acid salt of calcium ion, Since there exists a thing with a low decomposition temperature, it is preferable to select a thing as high as possible. Further, since the amount of calcium ion added is small, it is difficult to cause coloring, but a colorless substance is more preferable.
Specifically, for example, calcium acetate, calcium nitrate, calcium sulfate, calcium hydroxide, calcium ascorbate, calcium borate, calcium formate, calcium butyrate, calcium thiocyanate, calcium oxalate, calcium hypochlorite, calcium carbonate Calcium gluconate, calcium lactate, calcium phosphate, calcium chloride, etc., and as the salt to become an aqueous solution, calcium acetate, calcium nitrate, calcium carbonate, calcium gluconate, calcium lactate, calcium chloride, calcium hydroxide can be selected preferable.
上記バリウムイオンの有機酸塩又は無機酸塩としては、水溶液になる塩であれば特に限定されず、例えば、酢酸バリウム、塩化バリウム、硝酸バリウム、水酸化バリウム、チオシアン酸バリウム等が挙げられる。 The organic acid salt or inorganic acid salt of barium ions is not particularly limited as long as it is an aqueous solution salt, and examples thereof include barium acetate, barium chloride, barium nitrate, barium hydroxide, and barium thiocyanate.
本発明の合わせガラス用中間膜において、上記カルシウムイオン及び／又はバリウムイオンの含有量としては、下限は３０ｐｐｍ、上限は１２０ｐｐｍである。３０ｐｐｍ未満であると、本発明の合わせガラス用中間膜中に存在するカルシウムイオン及び／又はバリウムイオンの量が少なくなり、残留イオン成分を配位子として錯体を充分に形成することができず、本発明の合わせガラス用中間膜を用いて熱線反射合わせガラスや低反射合わせガラスを製造したときに、銀色の斑点が発生する。バリウムイオン及び／又はカルシウムイオンの含有量が１２０ｐｐｍを超えると、原因は明らかではないが、銀色の斑点の発生を促進してしまう。好ましい下限は３０ｐｐｍ、好ましい上限は９０ｐｐｍである。 In the interlayer film for laminated glass of the present invention, the content of the calcium ions and / or barium ions is 30 ppm at the lower limit and 120 ppm at the upper limit. If it is less than 30 ppm, the amount of calcium ions and / or barium ions present in the interlayer film for laminated glass of the present invention is reduced, and a complex cannot be sufficiently formed using the residual ion component as a ligand, When a heat ray reflective laminated glass or a low reflective laminated glass is produced using the interlayer film for laminated glass of the present invention, silver spots are generated. When the content of barium ions and / or calcium ions exceeds 120 ppm, the cause is not clear, but the occurrence of silver spots is promoted. A preferred lower limit is 30 ppm and a preferred upper limit is 90 ppm.
本発明の合わせガラス用中間膜は、紫外線吸収剤を含有することが好ましい。上記紫外線吸収剤としては特に限定されず、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、トリアジン系化合物、及び、ベンゾエート系化合物等が挙げられる。 The interlayer film for laminated glass of the present invention preferably contains an ultraviolet absorber. The ultraviolet absorber is not particularly limited, and examples thereof include benzotriazole compounds, benzophenone compounds, triazine compounds, and benzoate compounds.
本発明の合わせガラス用中間膜は、更に必要に応じて、紫外線吸収剤、光安定剤、界面活性剤、難燃剤、帯電防止剤、耐湿剤、熱線反射剤、熱線吸収剤等の従来公知の添加剤を含有してもよい。 If necessary, the interlayer film for laminated glass of the present invention may be a conventionally known material such as an ultraviolet absorber, a light stabilizer, a surfactant, a flame retardant, an antistatic agent, a moisture-resistant agent, a heat ray reflective agent, or a heat ray absorbent. An additive may be contained.
本発明の合わせガラス用中間膜の厚さの好ましい下限は１５０μｍ、好ましい上限は３０００μｍである。１５０μｍ未満であると、合わせガラスとした際に耐貫通性が低下することがあり、３０００μｍを超えると、合わせガラスとした際に全体として厚くなりすぎる。より好ましい下限は２５０μｍ、より好ましい上限は８００μｍである。 The preferable lower limit of the thickness of the interlayer film for laminated glass of the present invention is 150 μm, and the preferable upper limit is 3000 μm. When it is less than 150 μm, the penetration resistance may be lowered when a laminated glass is used. When it exceeds 3000 μm, the laminated glass is too thick as a whole. A more preferable lower limit is 250 μm, and a more preferable upper limit is 800 μm.
本発明の合わせガラス用中間膜を製造する方法としては特に限定されず、例えば、上述したマトリックス樹脂に、可塑剤、接着力調整剤、カルシウムイオン及び／又はバリウムイオン、並びに、必要に応じて添加する紫外線吸収剤等の所定量を添加した混合物を混合混練し成形する方法が挙げられる。 The method for producing the interlayer film for laminated glass of the present invention is not particularly limited. For example, it is added to the above-described matrix resin as a plasticizer, an adhesive strength modifier, calcium ions and / or barium ions, and if necessary. And a method of mixing and kneading and mixing a mixture to which a predetermined amount of an ultraviolet absorber or the like is added.
上記混合物の混練の方法としては特に限定されず、例えば、押出機、プラストゲラフ、ニーダー、バンバリーミキサー、カレンダーロール等を用いる方法が挙げられる。なかでも、連続的な生産に適することから、押出機を用いる方法が好適である。 The method for kneading the mixture is not particularly limited, and examples thereof include a method using an extruder, a Plastgeraf, a kneader, a Banbury mixer, a calendar roll, and the like. Especially, since it is suitable for continuous production, the method using an extruder is suitable.
上記成形の方法としては特に限定されず、例えば、押し出し法、カレンダー法、プレス法等が挙げられる。 The molding method is not particularly limited, and examples thereof include an extrusion method, a calendar method, and a pressing method.
本発明の合わせガラス用中間膜を用いてなる合わせガラスもまた、本発明の１つである。
本発明の合わせガラスは、本発明の合わせガラス用中間膜と、前記合わせガラス用中間膜を挟持する２枚のガラス板とを有する合わせガラスであって、少なくとも一方の前記ガラス板と合わせガラス用中間膜との界面に、銀層等の金属コーティング層が設けられている合わせガラスである。
Laminated glass using the interlayer film for laminated glass of the present invention is also one aspect of the present invention.
The laminated glass of the present invention is a laminated glass having the interlayer film for laminated glass of the present invention and two glass plates sandwiching the interlayer film for laminated glass, and is for at least one of the glass plate and the laminated glass. It is a laminated glass in which a metal coating layer such as a silver layer is provided at the interface with the intermediate film.
また、本発明の合わせガラスにおいて、本発明の合わせガラス用中間膜は単層膜であってもよく、多層膜であってもよい。本発明の合わせガラス用中間膜が多層膜である場合には、少なくとも一方の表層に接着力調整剤、カルシウムイオン及び／又はバリウムイオンを含有する層が形成されていればよい。更に、本発明の合わせガラス用中間膜が多層膜である場合には、本発明の合わせガラスは、本発明の合わせガラス用中間膜の接着力調整剤、カルシウムイオン及び／又はバリウムイオンを含有している表層と、ガラス板との界面に銀層等の金属コーティング層を有するように本発明の合わせガラスを製造するとよい。 In the laminated glass of the present invention, the interlayer film for laminated glass of the present invention may be a single layer film or a multilayer film. When the interlayer film for laminated glass of the present invention is a multilayer film, it is sufficient that a layer containing an adhesive force adjusting agent, calcium ions and / or barium ions is formed on at least one surface layer. Furthermore, when the interlayer film for laminated glass of the present invention is a multilayer film, the laminated glass of the present invention contains the adhesive force regulator, calcium ion and / or barium ion of the interlayer film for laminated glass of the present invention. The laminated glass of the present invention may be manufactured so as to have a metal coating layer such as a silver layer at the interface between the surface layer and the glass plate.
上記金属コーティング層としては特に限定されず、熱線反射合わせガラスや低反射合わせガラスに用いられる従来公知のものが挙げられる。 It does not specifically limit as said metal coating layer, The conventionally well-known thing used for heat ray reflective laminated glass and low reflection laminated glass is mentioned.
本発明の合わせガラスの製造方法としては特に限定されず、従来公知の合わせガラスの製造方法を用いることができる。 It does not specifically limit as a manufacturing method of the laminated glass of this invention, The manufacturing method of a conventionally well-known laminated glass can be used.
本発明の合わせガラスは、上記構成からなることから、合わせガラス用中間膜中の残留イオン成分による銀色の斑点の発生や合わせガラス用中間膜とガラス板との接着力の異常亢進を防ぐことができることから、例えば、自動車等のフロントガラス等として好適に用いることができる。 Since the laminated glass of the present invention has the above-described configuration, it is possible to prevent the occurrence of silver spots due to residual ion components in the interlayer film for laminated glass and the abnormal increase in the adhesive force between the interlayer film for laminated glass and the glass plate. Therefore, for example, it can be suitably used as a windshield of an automobile or the like.
本発明によれば、耐貫通性に優れ、合わせガラス用中間膜とガラス板との界面に、銀層等の金属コーティング層が設けられた合わせガラスとしたときに、銀色の斑点の発生を抑制することができる合わせガラス用中間膜、及び、該合わせガラス用中間膜を用いてなる合わせガラスを提供することができる。 According to the present invention, it has excellent penetration resistance and suppresses the occurrence of silver spots when a laminated glass is provided with a metal coating layer such as a silver layer at the interface between the interlayer film for laminated glass and the glass plate. An interlayer film for laminated glass that can be produced, and a laminated glass using the interlayer film for laminated glass can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
（１）マトリックス樹脂の合成
純水２８９０重量部に、平均重合度１７００、鹸化度９９．２モル％のポリビニルアルコール２７５重量部を加えて加熱溶解した。この反応系を１５℃に温度調節し、３５重量％の塩酸２０１重量部とｎ−ブチルアルデヒド１５７重量部とを加え、この温度を保持して反応物を析出させた。その後、反応系を６０℃で３時間保持して反応を完了させ、過剰の水で洗浄して未反応のｎ−ブチルアルデヒドを洗い流し、塩酸触媒を汎用な中和剤である水酸化ナトリウム水溶液で中和し、更に、過剰の水で２時間水洗及び乾燥を経て、白色粉末状のポリビニルブチラール樹脂を得た。この樹脂の平均ブチラール化度は６８．５モル％であった。
(Example 1)
(1) Synthesis of matrix resin To 2890 parts by weight of pure water, 275 parts by weight of polyvinyl alcohol having an average polymerization degree of 1700 and a saponification degree of 99.2 mol% was added and dissolved by heating. The temperature of this reaction system was adjusted to 15 ° C., 201 parts by weight of 35% by weight hydrochloric acid and 157 parts by weight of n-butyraldehyde were added, and this temperature was maintained to precipitate the reaction product. Thereafter, the reaction system is maintained at 60 ° C. for 3 hours to complete the reaction, washed with excess water to wash away unreacted n-butyraldehyde, and the hydrochloric acid catalyst is washed with a general-purpose neutralizing agent, sodium hydroxide aqueous solution. The mixture was neutralized, washed with excess water for 2 hours and dried to obtain a white powdery polyvinyl butyral resin. The average butyralization degree of this resin was 68.5 mol%.
（２）合わせガラス用中間膜の製造
得られたポリビニルブチラール樹脂１００重量部に対して、トリエチレングリコール−ジ−エチレンブチレート（３ＧＯ）４０重量部、酢酸マグネシウム水溶液０．１６４重量部、１５％酢酸バリウム水溶液０．２０５重量部を添加し、プラスト機にて混練し、押出機により金型よりシート状に押し出して、厚さ７４５μｍの合わせガラス用中間膜を得た。
得られた合わせガラス用中間膜中のマグネシウムイオン含有量、及び、バリウムイオン含有量をＩＣＰ発光元素分析で定量したところ、それぞれ３０ｐｐｍ、及び、１２０ｐｐｍであった。
(2) Production of interlayer film for laminated glass With respect to 100 parts by weight of the obtained polyvinyl butyral resin, 40 parts by weight of triethylene glycol-di-ethylene butyrate (3GO), 0.164 parts by weight of aqueous magnesium acetate solution, 15% 0.205 parts by weight of an aqueous barium acetate solution was added, kneaded in a plast machine, and extruded from a mold into a sheet by an extruder to obtain an interlayer film for laminated glass having a thickness of 745 μm.
When the magnesium ion content and barium ion content in the obtained interlayer film for laminated glass were quantified by ICP luminescent elemental analysis, they were 30 ppm and 120 ppm, respectively.
（３）合わせガラスの製造
得られた合わせガラス用中間膜を、その一方の面から金属コーティング層が施されたフロートガラス（縦３０ｃｍ×横３０ｃｍ×厚さ２．５ｍｍ）、もう一方の面から金属コーティング層の施されていないフロートガラス（縦３０ｃｍ×横３０ｃｍ×厚さ２．５ｍｍ）で挟み込み、これをゴムバック内に入れ、２．６ｋＰａの真空度で２０分間脱気した後、脱気したままオーブンに移し、更に９０℃で３０分間保持しつつ真空プレスした。このようにして予備圧着された合わせガラスをオートクレーブ中で１３５℃、圧力１．２ＭＰａの条件で２０分間圧着を行い、合わせガラスを得た。
(3) Manufacture of laminated glass The intermediate film for laminated glass thus obtained is float glass (length 30 cm x width 30 cm x thickness 2.5 mm) coated with a metal coating layer from one side, from the other side After sandwiching with float glass (length 30cm x width 30cm x thickness 2.5mm) without metal coating layer, this is put in a rubber bag and deaerated at a vacuum degree of 2.6 kPa for 20 minutes. As it was, it was transferred to an oven and further vacuum pressed while being kept at 90 ° C. for 30 minutes. The laminated glass preliminarily pressure-bonded in this manner was pressure-bonded for 20 minutes in an autoclave at 135 ° C. and a pressure of 1.2 MPa to obtain a laminated glass.
（実施例２）
バリウムイオン濃度が６０ｐｐｍとなるように１５％酢酸バリウム水溶液を添加した以外は、実施例１と同様にして合わせガラス用中間膜を製造し、該合わせガラス用中間膜を用いた以外は、実施例１と同様にして合わせガラスを製造した。
(Example 2)
Except that a 15% barium acetate aqueous solution was added so that the barium ion concentration would be 60 ppm, an interlayer film for laminated glass was produced in the same manner as in Example 1 and the interlayer film for laminated glass was used. A laminated glass was produced in the same manner as in Example 1.
（実施例３）
バリウムイオン濃度が３０ｐｐｍとなるように１５％酢酸バリウム水溶液を添加した以外は、実施例１と同様にして合わせガラス用中間膜を製造し、該合わせガラス用中間膜を用いた以外は、実施例１と同様にして合わせガラスを製造した。
(Example 3)
Except that a 15% barium acetate aqueous solution was added so that the barium ion concentration was 30 ppm, an interlayer film for laminated glass was produced in the same manner as in Example 1, and the interlayer film for laminated glass was used. A laminated glass was produced in the same manner as in Example 1.
（実施例４）
１５％酢酸バリウム水溶液に代えて、１５％の酢酸カルシウム水溶液０．２２重量部添加した以外は、実施例１と同様にして合わせガラス用中間膜を製造し、該合わせガラス用中間膜を用いた以外は、実施例１と同様にして合わせガラスを製造した。
得られた合わせガラス用中間膜のマグネシウムイオン含有量、及び、カルシウムイオン含有量をＩＣＰ発光元素分析で定量したところ、それぞれ３０ｐｐｍ、及び、６０ｐｐｍであった。
Example 4
An interlayer film for laminated glass was produced in the same manner as in Example 1 except that 0.22 parts by weight of 15% calcium acetate aqueous solution was added instead of the 15% barium acetate aqueous solution, and the interlayer film for laminated glass was used. Except for the above, laminated glass was produced in the same manner as in Example 1.
When the magnesium ion content and calcium ion content of the obtained interlayer film for laminated glass were quantified by ICP luminescent elemental analysis, they were 30 ppm and 60 ppm, respectively.
（実施例５）
カルシウムイオン濃度が３０ｐｐｍとなるように１５％の酢酸カルシウム水溶液を添加した以外は、実施例４と同様にして合わせガラス用中間膜を製造し、該合わせガラス用中間膜を用いた以外は、実施例４と同様にして合わせガラスを製造した。
(Example 5)
A laminated glass interlayer film was produced in the same manner as in Example 4 except that a 15% calcium acetate aqueous solution was added so that the calcium ion concentration was 30 ppm, and the laminated glass interlayer film was used except that the laminated glass interlayer film was used. A laminated glass was produced in the same manner as in Example 4.
（比較例１）
１５％酢酸バリウム水溶液を添加せず、マグネシウムイオン濃度が６０ｐｐｍとなるように酢酸マグネシウム水溶液を添加した以外は、実施例１と同様にして合わせガラス用中間膜を製造し、該合わせガラス用中間膜を用いて実施例１と同様にして合わせガラスを製造した。
(Comparative Example 1)
A laminated glass interlayer film was produced in the same manner as in Example 1 except that a 15% barium acetate aqueous solution was not added and a magnesium acetate aqueous solution was added so that the magnesium ion concentration was 60 ppm. A laminated glass was produced in the same manner as in Example 1.
（比較例２）
１５％酢酸バリウム水溶液を添加せず、塩化カルシウムを添加し、カルシウム濃度を１３０ｐｐｍとした以外は、実施例１と同様にして合わせガラス用中間膜を製造し、該合わせガラス用中間膜を用いて実施例１と同様にして合わせガラスを製造した。
(Comparative Example 2)
A laminated glass interlayer film was produced in the same manner as in Example 1 except that 15% barium acetate aqueous solution was not added, calcium chloride was added, and the calcium concentration was 130 ppm. A laminated glass was produced in the same manner as in Example 1.
（比較例３）
１５％酢酸カルシウム水溶液を添加し、カルシウムイオン濃度を１２０ｐｐｍとし、酢酸マグネシウムを添加しなかった以外は、実施例４と同様にして合わせガラス用中間膜を製造し、該合わせガラス用中間膜を用いて実施例４と同様にして合わせガラスを製造した。
(Comparative Example 3)
A laminated glass interlayer film was produced in the same manner as in Example 4 except that a 15% calcium acetate aqueous solution was added, the calcium ion concentration was 120 ppm, and magnesium acetate was not added. In the same manner as in Example 4, a laminated glass was produced.
（比較例４）
１５％酢酸カルシウム水溶液を添加し、カルシウムイオン濃度を６０ｐｐｍとし、酢酸マグネシウムを添加し、マグネシウム濃度を１０ｐｐｍとした以外は、実施例４と同様にして合わせガラス用中間膜を製造し、該合わせガラス用中間膜を用いて実施例４と同様にして合わせガラスを製造した。
(Comparative Example 4)
An interlayer film for laminated glass was produced in the same manner as in Example 4 except that a 15% calcium acetate aqueous solution was added, the calcium ion concentration was 60 ppm, magnesium acetate was added, and the magnesium concentration was 10 ppm. A laminated glass was produced in the same manner as in Example 4 using the intermediate film.
実施例１〜５及び比較例１〜４で製造した合わせガラスについて、以下の評価を行った。 The following evaluation was performed about the laminated glass manufactured in Examples 1-5 and Comparative Examples 1-4.
（銀色の斑点の有無）
実施例１〜５及び比較例１〜４で製造した合わせガラスの銀色の斑点の有無を目視で確認した後、１００℃のドライオーブンに入れ、２４時間、４８時間、６０時間、１２０時間、２００時間経過後における銀色の斑点の有無を目視にて確認した。結果を表１に示す。なお、表１中、「◎」は、５ｃｍ四方内に銀色の斑点が確認されなかったことを示し、「○」は、５ｃｍ四方内に１ｍｍ以上の銀色の斑点が確認されず１ｍｍ以下の銀色の斑点も３個以下であったことを示し、「×」は、５ｃｍ四方内に１ｍｍ以上の銀色の斑点又は、１ｍｍ未満の銀色の斑点が４個以上確認されたことを示す。
(With or without silver spots)
After visually confirming the presence or absence of silver spots on the laminated glasses produced in Examples 1 to 5 and Comparative Examples 1 to 4, they were placed in a dry oven at 100 ° C., 24 hours, 48 hours, 60 hours, 120 hours, 200 hours. The presence or absence of silver spots after the passage of time was visually confirmed. The results are shown in Table 1. In Table 1, “◎” indicates that no silver spot was confirmed in a 5 cm square, and “◯” indicates a silver spot of 1 mm or less without a silver spot of 1 mm or more in a 5 cm square. The number of spots was 3 or less, and “x” indicates that 4 or more silver spots of 1 mm or more or silver spots of less than 1 mm were confirmed in 5 cm square.
（合わせガラス用中間膜のパンメル値の測定）
合わせガラスを−１８℃±０．６℃の温度に１６時間調整し、この合わせガラスの中央部（縦１５０ｍｍ×横１５０ｍｍの部分）を頭部が０．４５ｋｇのハンマーで打って、ガラスの粒径が６ｍｍ以下になるまで粉砕し、ガラスが部分剥離した後の膜の露出度を測定し、下記表２によりパンメル値を求めた。なお、測定は合わせガラス作製直後と合わせガラス作製２ヶ月後に行い、時間経過に伴う合わせガラス用中間膜とガラスとの耐貫通性を評価した。なお、表１中、「○」は、パンメル値が３〜６であることを示し、「×」は、パンメル値が０〜２又は７〜８であることを示す。
(Measurement of Pummel value of interlayer film for laminated glass)
The laminated glass was adjusted to a temperature of −18 ° C. ± 0.6 ° C. for 16 hours. After crushing until the diameter was 6 mm or less, the degree of exposure of the film after the glass was partially peeled was measured, and the Pummel value was obtained from Table 2 below. The measurement was performed immediately after the laminated glass was produced and 2 months after the laminated glass was produced, and the penetration resistance between the interlayer film for laminated glass and the glass over time was evaluated. In Table 1, “◯” indicates that the Pummel value is 3 to 6, and “x” indicates that the Pummel value is 0 to 2 or 7 to 8.
本発明によれば、合わせガラス用中間膜とガラス板との界面に銀層等の金属コーティング層が設けられた合わせガラスとしたときに、銀色の斑点の発生を抑制することができ、耐貫通性に優れた合わせガラス用中間膜、及び、該合わせガラス用中間膜を用いてなる合わせガラスを提供することができる。 According to the present invention, when the laminated glass is provided with a metal coating layer such as a silver layer at the interface between the interlayer film for laminated glass and the glass plate, it is possible to suppress the occurrence of silver spots and to prevent penetration. An interlayer film for laminated glass having excellent properties and a laminated glass formed using the interlayer film for laminated glass can be provided.
Claims (2)
前記接着力調整剤の含有量が２０〜６０ｐｐｍであり、前記カルシウムイオン及び／又はバリウムイオンの含有量が３０〜１２０ｐｐｍである
ことを特徴とする合わせガラス用中間膜。 An interlayer film for laminated glass containing a matrix resin, a plasticizer, an adhesive force regulator, and calcium ions and / or barium ions,
The interlayer film for laminated glass, wherein the adhesive strength adjusting agent content is 20 to 60 ppm, and the calcium ion and / or barium ion content is 30 to 120 ppm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014024313A (en) * | 2011-12-12 | 2014-02-06 | Sekisui Chem Co Ltd | Luminescent sheet, intermediate film for laminated glass, laminated glass, and display device |
| JPWO2016056668A1 (en) * | 2014-10-10 | 2017-07-20 | 積水化学工業株式会社 | Laminated glass interlayer film and laminated glass |
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| JPH06144891A (en) * | 1992-11-10 | 1994-05-24 | Sekisui Chem Co Ltd | Heat ray reflection glass |
| JPH07309642A (en) * | 1994-05-16 | 1995-11-28 | Sekisui Chem Co Ltd | Middle layer for laminated glass and laminated glass |
| JPH10273345A (en) * | 1997-01-28 | 1998-10-13 | Sekisui Chem Co Ltd | Interlayer for laminated glass and laminated glass using the same |
| JP2002516201A (en) * | 1998-05-22 | 2002-06-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Elimination of difference in adhesiveness depending on glass direction in laminated safety glass |
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- 2006-07-31 JP JP2006207757A patent/JP4758844B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06144891A (en) * | 1992-11-10 | 1994-05-24 | Sekisui Chem Co Ltd | Heat ray reflection glass |
| JPH07309642A (en) * | 1994-05-16 | 1995-11-28 | Sekisui Chem Co Ltd | Middle layer for laminated glass and laminated glass |
| JPH10273345A (en) * | 1997-01-28 | 1998-10-13 | Sekisui Chem Co Ltd | Interlayer for laminated glass and laminated glass using the same |
| JP2002516201A (en) * | 1998-05-22 | 2002-06-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Elimination of difference in adhesiveness depending on glass direction in laminated safety glass |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014024313A (en) * | 2011-12-12 | 2014-02-06 | Sekisui Chem Co Ltd | Luminescent sheet, intermediate film for laminated glass, laminated glass, and display device |
| JPWO2016056668A1 (en) * | 2014-10-10 | 2017-07-20 | 積水化学工業株式会社 | Laminated glass interlayer film and laminated glass |
| JP2020097518A (en) * | 2014-10-10 | 2020-06-25 | 積水化学工業株式会社 | Interlayer for glass laminate and glass laminate |
| US11453194B2 (en) | 2014-10-10 | 2022-09-27 | Sekisui Chemical Co., Ltd. | Interlayer film for laminated glass, and laminated glass |
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