CN102886952B - Comprise the film laminates with damping capacity of the sublayer being made up of polyvinyl alcohol contracting (different) aldehyde of plasticizer-containing - Google Patents
Comprise the film laminates with damping capacity of the sublayer being made up of polyvinyl alcohol contracting (different) aldehyde of plasticizer-containing Download PDFInfo
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- CN102886952B CN102886952B CN201210252492.4A CN201210252492A CN102886952B CN 102886952 B CN102886952 B CN 102886952B CN 201210252492 A CN201210252492 A CN 201210252492A CN 102886952 B CN102886952 B CN 102886952B
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- polyvinyl alcohol
- aldehyde
- different
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- film laminates
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 142
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 135
- 239000004014 plasticizer Substances 0.000 title claims abstract description 37
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 13
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 134
- 239000011521 glass Substances 0.000 claims abstract description 31
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 29
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- -1 polyethylene Polymers 0.000 claims description 33
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000004698 Polyethylene (PE) Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 65
- 150000001299 aldehydes Chemical class 0.000 description 63
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 34
- 150000002148 esters Chemical class 0.000 description 17
- 229920002689 polyvinyl acetate Polymers 0.000 description 17
- 239000011118 polyvinyl acetate Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 1-butanal Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 10
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N Triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- IMROMDMJAWUWLK-UHFFFAOYSA-N ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 7
- AMIMRNSIRUDHCM-UHFFFAOYSA-N isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000002194 synthesizing Effects 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 5
- 238000011068 load Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 229960000250 adipic acid Drugs 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 4
- 230000001264 neutralization Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PYGXAGIECVVIOZ-UHFFFAOYSA-N dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 3
- 229940031954 dibutyl sebacate Drugs 0.000 description 3
- HHECSPXBQJHZAF-UHFFFAOYSA-N dihexyl hexanedioate Chemical compound CCCCCCOC(=O)CCCCC(=O)OCCCCCC HHECSPXBQJHZAF-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N Phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M Potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive Effects 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- VVKREWPWSWPBGC-UHFFFAOYSA-N benzoic acid;2-(2-hydroxypropoxy)propan-1-ol Chemical compound CC(O)COC(C)CO.OC(=O)C1=CC=CC=C1 VVKREWPWSWPBGC-UHFFFAOYSA-N 0.000 description 2
- ZWYAVGUHWPLBGT-UHFFFAOYSA-N bis(6-methylheptyl) decanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCCCCCC(=O)OCCCCCC(C)C ZWYAVGUHWPLBGT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 101700000038 mpas Proteins 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- DLZBUNUDESZERL-UHFFFAOYSA-N 1-O-heptyl 6-O-nonyl hexanedioate Chemical compound CCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCC DLZBUNUDESZERL-UHFFFAOYSA-N 0.000 description 1
- GWQRPOCMBMQBTK-UHFFFAOYSA-N 2-[2-(2-ethylhexanoyloxy)ethoxy]ethyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCCOCCOC(=O)C(CC)CCCC GWQRPOCMBMQBTK-UHFFFAOYSA-N 0.000 description 1
- UZNLHJCCGYKCIL-UHFFFAOYSA-M 6-ethoxy-6-oxohexanoate Chemical class CCOC(=O)CCCCC([O-])=O UZNLHJCCGYKCIL-UHFFFAOYSA-M 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Benzyl butyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N Dihydroxyacetone Chemical class OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N Diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 241000214474 Doa Species 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N Glyoxalate, Glyoxylate Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 102100019911 POLK Human genes 0.000 description 1
- 101700060162 POLK Proteins 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N Sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 210000001138 Tears Anatomy 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N Tetraethylene glycol dimethyl ether Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003078 antioxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000002146 bilateral Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- AYWLCKHHUFBVGJ-UHFFFAOYSA-N bis(7-methyloctyl) hexanedioate Chemical compound CC(C)CCCCCCOC(=O)CCCCC(=O)OCCCCCCC(C)C AYWLCKHHUFBVGJ-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000003750 conditioning Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 239000004806 diisononylester Substances 0.000 description 1
- NEHDRDVHPTWWFG-UHFFFAOYSA-N dioctyl hexanedioate Chemical compound CCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC NEHDRDVHPTWWFG-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000001771 impaired Effects 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-M nonanoate Chemical compound CCCCCCCCC([O-])=O FBUKVWPVBMHYJY-UHFFFAOYSA-M 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003534 oscillatory Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
The present invention relates to comprise the film laminates with damping capacity of the sublayer being made up of polyvinyl alcohol contracting (different) aldehyde of plasticizer-containing.Specifically, the present invention relates to a kind of film laminates, become with C-shaped with layer A, B of at least one Pioloform, polyvinyl acetal by each at least one plasticizer self-contained of at least three, two of which outer layer A and C comprises the identical or different Pioloform, polyvinyl acetal of at least one PVA-based ratio with 18.5 to 23 weight %, at least one inner layer B comprises the Pioloform, polyvinyl acetal of the PVA-based ratio with 12 to 18 weight %, and at least one of layer A, B or C comprises at least one polyvinyl alcohol contracting (different) aldehyde.This film laminates may be used for manufacturing for automobile, aircraft, boats and ships, architectural glazings, the glass film layered product/glass composite of facade parts, or is used for manufacturing photovoltaic module.
Description
Technical field
The present invention relates to one be such as suitable as in composite safe glass (Verbundsicherheitsgl ser)
The film laminates in intermediate layer, described film laminates is by least three polyvinyl alcohol based on plasticizer-containing contracting (just) aldehyde
The layer of (Polyvinyl (n) acetal) and/or polyvinyl alcohol contracting (different) aldehyde (Polyvinyl (iso) acetal) is formed and to sound
The damping capacity that sound has had.
The present invention relates to the film laminates in a kind of intermediate layer being such as suitable as in composite safe glass, described film is laminated
Body is formed by the layer of at least three polyvinyl alcohol based on plasticizer-containing contracting (just) aldehyde and/or polyvinyl alcohol contracting (different) aldehyde and is had
Excellent penetration performance (Penetrationseigenschaft).
Prior art
Composite safe glass is generally made up of the intermediate coat of two glass plates and connection glass plate.Mainly make as membrane material
With the polyvinyl butyral resin (PVB) of plasticizer-containing, it can react acquisition by making polyvinyl alcohol and hutanal.
The feature become more and more important of compound window glass is its sound insulation value, and it can be adjusted by corresponding interlayer film
Joint.
To this end, the commonly used intermediate coat with 2 to 5 sublayers, the most each sublayer has difference in terms of its mechanical strength,
And realize sound insulation from there through mechanical decoupled conjunction.
Can such as by PVA-based in the plasticizer loading of described film or the Pioloform, polyvinyl acetal of use or
The ratio of polyvinyl acetate ester group, sets the different mechanical strengths of the film of Pioloform, polyvinyl acetal based on plasticizer-containing.
Generally, the mechanical strength of PVB film can be passed through in its plasticizer loading, or the Pioloform, polyvinyl acetal by use
Polyvinyl alcohol group or the ratio of polyvinyl acetate ester group regulated.
Such as, therefore US 5,340,654 or WO 2006/102049 describes multilayer system, and wherein ground floor comprises and has
The polyvinyl butyral resin of high residue acetate content, the second layer comprises the polyvinyl alcohol contracting fourth with low-residual acetate content
Aldehyde.
Similarly, WO 2008/137367 describes multilayer system, the sublayer being wherein made up of polyvinyl butyral resin
(Teilschicht) different in terms of polyvinyl alcohol content.
Due to different residual acetate content and/or different polyvinyl alcohol group ratios, each sublayer has different
Plasticizer loading, and therefore there is different mechanical strengths.It is achieved in mechanical decoupled conjunction and the sound insulation therefore improved.
Known multilayer film is based on the polyvinyl butyral resin that can obtain by making polyvinyl alcohol and hutanal react.Use
There is polyvinyl alcohol contracting (just) butyraldehyde of different polyvinyl alcohol or polyvinyl acetate contents, it is thus achieved that the different plasticizer of each layer
Content.The mechanical performance so causing each layer is different, and these differences are the biggest, and the sound insulation of layered product is the best.Excellent sound insulation is usual
Cause the mechanical performance of difference.Additionally, each layer is incompatible, there's almost no mechanical adhesion the most betwixt, and may be each other
Relatively slide.Incompatible each layer no longer can be mixed with each other, and therefore these film laminates can only be recycled in technique with differing from.
Therefore the purpose of the present invention is the film laminates manufacturing and having sound insulation value, due to gathering the plasticizer-containing used
Vinyl acetal is selected, and described film has high plasticizer compatbility and therefore shows excellent sound insulation.
Have now unexpectedly been found that the film laminates comprising at least one layer based on polyvinyl alcohol contracting (different) aldehyde has excellent
Plasticizer compatbility and owing to different mechanical strengths has excellent damping capacity.
Do not use the film laminates of polyvinyl alcohol contracting (different) aldehyde such as by WO 2006/102049 A1, WO 2011/
078314 A1, WO 2011/081190 A1, WO 2011/024788 A1, US 2007014976 and JP 2011042552
Know.The advantageous property of polyvinyl alcohol contracting (different) aldehyde is not the most described.
Present invention is accordingly directed to the film laminates become by least three layer A, B with C-shaped, each layer comprises at least one plasticizer
With at least one Pioloform, polyvinyl acetal, wherein
-two outer layer A with C comprise the most identical of at least one PVA-based ratio with 18.5 to 23 weight %
Or different Pioloform, polyvinyl acetals
-at least one inner layer B comprises the Pioloform, polyvinyl acetal of the PVA-based ratio with 12 to 18 weight %, and
At least one of-layer A, B or C comprises at least one polyvinyl alcohol contracting (different) aldehyde.
The film laminates of the present invention preferably containing at least one, particularly two are contracted (just) containing at least one polyvinyl alcohol
The layer of aldehyde.Therefore, the film laminates of the present invention can have at least one, and particularly two comprise the contracting of at least one polyvinyl alcohol
The layer of (different) aldehyde.
In this flexible program of the present invention, film laminates can be formed by this way so that two outer layer A and
C comprises polyvinyl alcohol contracting (different) aldehyde that at least one is the most identical or different, and inner layer B comprises at least one polyvinyl alcohol contracting (just)
Aldehyde.Alternatively, two outer layer A and C can comprise at least one the most identical or different polyvinyl alcohol contracting (just) aldehyde, and internal layer
B can comprise at least one polyvinyl alcohol contracting (different) aldehyde.
In another embodiment of the present invention, the film laminates of the present invention can be only by comprising at least one polyethylene
Layer A, B of alcohol contracting (different) aldehyde become with C-shaped, and i.e. two outer layer A and C comprise at least one the most identical or different polyvinyl alcohol contracting
(different) aldehyde, and inner layer B comprises at least different from layer A and C polyvinyl alcohol contracting (different) aldehyde.
According to ISO 16940:2008, based on damping capacity, to by 0.8 be laminated between two glass plates thick for 2 mm
The test sample that interlayer film thick for mm is formed measures the deadening of the film laminates of the present invention.Measure first in every case
Pattern.
The deadening of the film laminates of the present invention should be maximum at a temperature of the application of follow-up glass laminate.At vapour
In glass for vehicle window, because plate is heated in the winter time, freeze by air conditioning system in summer, so application temperature is about 20 DEG C.?
During above-mentioned measurement is arranged, preferably the temperature range of 17.5 to 22.5 DEG C, the damping of the film display maximum of the present invention, particularly hinders
Buddhist nun's value for more than 19%, preferably greater than 20% and more preferably above 23%.
Each layer that the present invention uses comprises by every case with " n-" (i.e. straight chain compound) or " iso-" aldehydes or ketones
Compound (i.e. branched chain compound) makes the Pioloform, polyvinyl acetal that Polyvinyl acetal obtains.
Polyvinyl alcohol contracting (different) aldehyde that the present invention uses is preferably by making at least one polyvinyl alcohol wrap with one or more
Containing 4 to 10 carbon atoms and there is at the α position or β position of ketone groups at least one branched aliphatic ketone compound reaction obtain
?.The aliphatic ketone compound being used for manufacturing polyvinyl alcohol contracting (different) aldehyde in layers can be identical or different.Poly-for manufacturing
The aliphatic ketone compound of vinyl alcohol contracting (different) aldehyde is the most identical；Polyvinyl alcohol contracting (different) in different layers
Aldehyde is the most chemically uniform, and i.e. they have identical PVA-based and polyvinyl acetate ester group ratio and identical
The degree of polymerization.Especially, isobutylaldehyde is used to manufacture polyvinyl alcohol contracting (different) aldehyde.
When manufacturing polyvinyl alcohol contracting (different) aldehyde that the present invention uses, in addition to described side chain ketonic compound, it is possible to additionally
Use one or more nonbranched aliphatic ketone compounds comprising 2 to 10 carbon atoms for acetalation.Just it is preferably used
The mixture of butyraldehyde and/or acetaldehyde and isobutylaldehyde.Acetal radical in polyvinyl alcohol contracting (different) aldehyde produced by side chain ketonic compound
Ratio should be greater than 60 mol% of branched and nonbranched acetal radical summation, preferably greater than 80 mol%.
The present invention use polyvinyl alcohol contracting (just) aldehyde especially by least one polyvinyl alcohol with one or more comprise 2 to
The aliphatic nonbranched ketonic compound reaction of 10 carbon atoms produces.Hutanal is preferably used for this.
When manufacturing polyvinyl alcohol contracting (just) aldehyde that the present invention uses, in addition to described nonbranched ketonic compound, it is possible to
Additionally use one or more branced aliphatic ketonic compounds comprising 4 to 10 carbon atoms for acetalation.Just it is preferably used
The mixture of butyraldehyde and/or acetaldehyde and isobutylaldehyde.Contracting in polyvinyl alcohol contracting (just) aldehyde produced by nonbranched ketonic compound
Aldehyde radical ratio should be greater than 60 mol% of branched and nonbranched acetal radical summation, preferably greater than 80 mol%.
In the different layers manufacturing Pioloform, polyvinyl acetal (polyvinyl alcohol contracting (different) aldehyde and polyvinyl alcohol contracting (just) aldehyde)
Polyvinyl alcohol can be the most identical or different, for the form of pure material or for have the different degree of polymerization or degree of hydrolysis
The form of mixtures of polyvinyl alcohol.
The poly-acetic acid second of the Pioloform, polyvinyl acetal (polyvinyl alcohol contracting (different) aldehyde and polyvinyl alcohol contracting (just) aldehyde) in different layers
Alkene ester content can be hydrolyzed into the polyvinyl alcohol of corresponding proportion by use and regulate.The polarity of Pioloform, polyvinyl acetal is by poly-acetic acid
The impact of vinyl acetate content, plasticizer compatbility and the mechanical strength of the most each sub-film also change.Be used as multiple aldehyde or
The mixture of ketonic compound carries out the acetalation of polyvinyl alcohol.
Each layer preferably comprises based on this layer, and polyvinyl acetate ester group ratio is the most identical or different, is 0.1 to 15 weight
Amount %, polyvinyl alcohol contracting (different) aldehyde of preferably 0.1 to 8 weight % and particularly 0.1 to 3 weight % and/or polyvinyl alcohol contracting (just)
Aldehyde.The polyvinyl acetate ester group ratio of 0.1 to 2 weight % is the most particularly preferred.
Layer A and C preferably comprises based on each layer, has the most identical or different PVA-based of 19.0 to 21 weight %
Polyvinyl alcohol contracting (different) aldehyde of ratio and/or polyvinyl alcohol contracting (just) aldehyde.Layer B preferably comprise based on described layer, have 14.0 to
Polyvinyl alcohol contracting (different) aldehyde of the PVA-based ratio of 16.0 weight % or 16.1 to 18 weight % and/or polyvinyl alcohol contracting (just)
Aldehyde.
Each layer preferably comprises uncrosslinked polyvinyl alcohol contracting (different) aldehyde and/or polyvinyl alcohol contracting (just) aldehyde.It is used as handing over
Polyvinyl alcohol contracting (different) aldehyde of connection and/or polyvinyl alcohol contracting (just) aldehyde of crosslinking.The method of cross-linked pioloform such as exists
EP 1527107 B1 and WO 2004/063231 A1 (wraps the hot self-crosslinking of carboxylic Pioloform, polyvinyl acetal), EP
1606325 A1 (with the Pioloform, polyvinyl acetal of polyacetals crosslinking) and the WO 03/020776 A1 (polyethylene with glyoxalic acid crosslinking
Acetal) described in.
The polyvinyl alcohol using crosslinking in inner layer B contract (different) aldehyde and/or crosslinking polyvinyl alcohol contracting (just) aldehyde be special
Preferably.In this case, using compared with the material that each is uncrosslinked especially, solution viscosity increases by the crosslinking of 25 to 200%
Polyvinyl alcohol contracting (different) aldehyde and/or crosslinking polyvinyl alcohol contracting (just) aldehyde.Such as, therefore uncrosslinked material can have 80
The solution viscosity of mPas, the material of crosslinking can have the solution viscosity of 100 to 250 mPas.According to WO 03/020776 A1,
It is applicable to manufacture crosslinking with the common polyvinyl alcohol of acetalization of the mixture of above-mentioned ketonic compound and dialdehyde or three aldehyde, such as glutaraldehyde
Polyvinyl alcohol contracting (different) aldehyde and polyvinyl alcohol contracting (just) aldehyde.
The Pioloform, polyvinyl acetal (polyvinyl alcohol contracting (different) aldehyde and polyvinyl alcohol contracting (just) aldehyde) used in layer A, B and C is permissible
Have less than 3000, the identical or different average degree of polymerization of preferably 200 to 2800.Preferably, use in layer A, B and C is poly-
Vinyl acetal (polyvinyl alcohol contracting (different) aldehyde or polyvinyl alcohol contracting (just) aldehyde) has the average degree of polymerization of 900 to 2500.
Generally, the compatibility between plasticizer and Pioloform, polyvinyl acetal reduces along with the decline of plasticizer polarity.Therefore
Compared with those plasticizers with relatively low polarity, the plasticizer with high polarity is the most compatible with Pioloform, polyvinyl acetal.
It addition, the compatibility of the plasticizer of low polarity rises along with acetalizing degree and improves, i.e. along with hydroxy number declines and thus gathers
Vinyl acetal polarity declines and improves.
Due to the different Pioloform, polyvinyl acetal group (just with different) of each layer, described layer can be identical PVA-based
Accommodate different plasticising dosage in the case of group's number, there is no plasticizer exudation or migration.Different plasticising dosage also causes each layer
Mechanical performance is different, therefore layer mechanical performance and thus film laminates mechanical performance can by selection plasticizer and/or
The polyvinyl alcohol content of the Pioloform, polyvinyl acetal used regulates.
Each layer can each self-contained identical or different plasticizer (first, second or the 3rd).Useization in all layers
Plasticizer identical on is preferred.
Each layer can comprise the plasticizer of following plasticizer becoming known for PVB film from least one or plasticizer mixing
Thing:
-polyhydric aliphatic race or the ester of aromatic acid, such as hexanedioic acid dialkyl ester, such as dihexyl adipate, adipic acid
Dioctyl ester, adipic acid hexyl cyclohexyl, adipic acid-heptyl ester and the mixture of nonyl ester, diisononyl adipate, adipic acid heptyl nonyl
Ester, and the ester of the ester alcohol of adipic acid and alicyclic ester alcohol or ether-containing key, DAS di alkyl sebacate, such as dibutyl sebacate, and
The ester of the ester alcohol of decanedioic acid and alicyclic ester alcohol or ether-containing key, the ester of phthalic acid, phthalic acid butyl benzyl ester or
Double-2-the butoxyethyl of phthalic acid, the ester of cyclohexane dicarboxylic acid, such as 1,2-cyclohexane dicarboxylic acid dinonyl
-there is the one or more unbranched or polyhydric aliphatic race of branced aliphatic or aromatic substituents or aromatic series
Alcohol or the ester of oligo-ether glycol or ether, such as diethylene glycol, 2,2'-ethylenedioxybis(ethanol). or tetraethylene glycol (TEG) and straight chain or branced aliphatic or alicyclic carboxylic
The ester of acid；The example of later group is it can be mentioned that diethylene glycol-bis--(2-ethylhexanoate), 2,2'-ethylenedioxybis(ethanol) .-bis--(2 ethyl hexanoic acid
Ester), 2,2'-ethylenedioxybis(ethanol) .-bis--(2 Ethylbutanoic acid ester), tetraethylene glycol (TEG)-bis--positive heptanoate, 2,2'-ethylenedioxybis(ethanol) .-bis--positive heptanoate, 2,2'-ethylenedioxybis(ethanol) .-bis--
N-caproate, tetraethylene glycol dimethyl ether and/or dipropyleneglycol benzoate
-there is aliphatic or aromatic ester alcohol phosphate, such as three (2-ethylhexyl) phosphate ester (TOF), tricresyl phosphate
Ethyl ester, diphenyl-ethylhexyl dihydrogen phosphate, and/or tricresyl phosphate
The ester of-citric acid, succinic acid and/or fumaric acid.
Particularly preferably one or more following plasticizers of use: Diisooctyl Sebacate (DOS), adipic acid two-2-
Octyl Nitrite (DOA), dihexyl adipate (DHA), dibutyl sebacate (DBS), 2,2'-ethylenedioxybis(ethanol) .-bis--positive heptanoate (3G7), four
Glycol-bis--positive heptanoate (4G7), 2,2'-ethylenedioxybis(ethanol) .-bis--2-ethylhexanoate (3GO or 3G8), tetraethylene glycol (TEG)-bis--n-2-ethyl hexyl
Acid esters (4GO or 4G8), two-2-butoxyethyl group adipate ester (DBEA), two-2-Butoxyethoxy ethyl adipate esters
(DBEEA), two-2-butoxyethyl group sebacate (DBES), two-2-ethylhexyl phthalate (DOP), two-different nonyl
Base phthalic acid ester (DINP), 2,2'-ethylenedioxybis(ethanol) .-bis--different pelargonate, 2,2'-ethylenedioxybis(ethanol) .-bis--2-propyl group alkyl caproates, 1,2-hexamethylene dicarboxyl
Acid diisononyl esters (DINCH), three (2-ethylhexyl) phosphate ester (TOF) and dipropyleneglycol benzoate.
Additionally, each layer can comprise other additive, such as quantity of residual, UV absorbent, antioxidant, adhesiveness regulates
Agent, fluorescent whitening agent, stabilizer, coloring agent, processing aid, organic or inorganic nano-particle, pyrolytic silicon dioxide and/or surface
Active substance.
In a kind of flexible program of the present invention, all layers comprise above-mentioned additive with essentially identical concentration.At this
In bright a kind of particular variation scheme, at least one layer does not comprise any adhesiveness regulator (antiplastering aid).In the scope of the invention
In, antiplastering aid is understood to mean that the Polyvinyl acetal film that can use it to the regulate plasticizer-containing adhesiveness to glass surface
Compound.This compounds is well known by persons skilled in the art；Alkali metal for this most commonly used organic acid
Or alkali salt, such as potassium acetate/magnesium.
For improving rigidity, at least one layer also can comprise 0.001 to 20 weight %, preferably 1 to 15 weight %, particularly 5 to
The SiO of 10 weight %2, it is optionally doped with Al2O3Or ZrO2。
Each layer in film laminates can almost use with any thickness, and condition is not change sound-proofing in disadvantageous mode
Energy.Therefore all layers can have identical thickness, but each layer of different-thickness also be can be combined.With three layers of complex form
Inventive film layered product preferably layout in, outer layer A and C has identical thickness substantially, and puigging B can be as much as possible
Thin.Therefore puigging B can have the thickness of 0.05 to 0.20 mm in the case of the gross thickness of film laminates is 0.76 mm.
The film laminates of the present invention preferably has the gross thickness of industrial routine, and such as 0.38,0.76 and 1.14 mm are (i.e.
Many times of 0.38 mm).
For manufacturing the film laminates of the present invention, each layer can first pass through extrusion and manufacture respectively, the most such as by together
It is wound up in film roll and mechanically engages, form the interlayer film of the present invention.Also can by while each layer of coextrusion manufacture film layer
Laminate.It is, for example possible to use multilamellar nozzle or the feed block of equipment carry out coextrusion for this.
In automotive field, it is often used in upper area the film with what is called " colour band ".To this end, the top of film is permissible
With the polymer melt coextrusion coloured for this, or in multilayer system, one of each layer can different colors.At this
In bright, this point can realize by completely or partially making at least one layer of coloring.
Film laminates or each layer of the present invention are generally manufactured by extrusion or co-extrusion, and (melted at certain condition
Pressure, melt temperature and mold temperature) under formed melt fractured surface, the most random surface roughness.
It is alternatively possible to be imprinted with this that process (Pr gevorgang) makes to have manufactured between at least one pair of roller
Bright film laminates imprints with regular nonrandom roughness.The film of impressing generally shows during compound glass manufacture
The exhaust performance (Entl ü ftungsverhalten) improved, and it is preferred for automotive field.Independent of manufacture method, this
Bright film laminates has and is applied to side or the more preferably surface texture on bilateral, and described surface texture has 15 to 150 μ
M, preferably 15 to 100 μm, more preferably 20 to 80 μm, and roughness R of particularly 40 to 75 μmz。
The principle manufacture of film based on Pioloform, polyvinyl acetal and composition are at such as EP 185 863 B1, EP 1 118
258 B1, WO 02/102591 A1, EP 1 118 258 described in B1 or EP 387 148 B1.
The film laminates of the present invention is suitable for manufacturing glass film layered product/glass, glass film layered product/plastics are combined
Body, or plastics/film laminates/Plastic composite body.Especially, the plastic plate being made up of Merlon, PET or PMMA is used.
Film laminates is particularly well-suited to manufacture for automobile, aircraft, boats and ships, architectural glazings, the glass film of facade parts
Layered product/glass, glass film layered product/Plastic composite body, or plastics/film laminates/Plastic composite body, or be used for manufacturing light
Volt module.
Especially, the film laminates of the present invention can be by mode well known by persons skilled in the art and one or more glass
Glass flaggy pressure, is used for manufacturing composite safe glass.Composite safe glass may be used for automotive field, is used for example as windshield,
With for building field, such as window or transparent facade parts, or it is used for manufacturing furniture.
For having the functional windshield of HUD, advantageously provide at least one layer of A, B or the C with wedge-shaped cross section.
Especially, layer B has wedge-shaped cross section and layer A with C has uniformly (face is parallel) section.
Detailed description of the invention
Measuring method
According to ASTM D 1396-92Measure polyvinyl alcohol content and the polyvinyl acetate contents of PVB.Acetalizing degree (=
Butyral content) can total as the polyvinyl alcohol content measured according to ASTM D 1396-92 and polyvinyl acetate contents
Calculate with the differential section of distance 100.By formula well known by persons skilled in the art, weight % is converted into mol%.
By being dissolved in ethanol by film, and follow-up quantitative gas chromatography method determines filmPlasticizer loading.For
Determine the plasticizer loading of each sub-film, it is necessary to after the conditioning time of about a week, i.e. the most basic in the migration of plasticizer
After end, multilayer film is the most separated, and measures respectively.
The measurement of damping capacity
By according to ISO 16940:2008, measuring the damping capacity of machinery impedance measuring film.To this end, film is laminated to 2
Between two glass plates that mm is thick, and therefrom cut lengths are the sample of 300 × 25 mm.By means of the cyano group third in reagent
Bonding ailhead screw (UA0866 type/Br ü el & Kjaer) is put on this glass specimen by olefin(e) acid ester adhesive, and so making can
By means of screw thread, sample is connected directly to reluctance head (8001 types/Br ü el & Kjaer GmbH).So can 1 to 10,
Measure the power at the point of glass specimen and acceleration in the frequency range of 000 Hz simultaneously.Reluctance head is directly placed at vibration swash
Send out device (4809 types/Br ü el & Kjaer GmbH) sway on platform, transmit required power whereby.To both be placed on can
In the heat insulation heating cupboard (Binder company) of regulation, so make to measure damping and amortization the temperature range of preferably 0 to 40 DEG C
Energy.Manufacture by means of noise signal generator (PULSE Frontend type 3560B-040/Br ü el & Kjaer GmbH) now
Noise, this noise signal generator also serves as signal receiver.Noise is via power amplifier (2718 types/Br ü el &
Kjaer GmbH) it is sent to oscillatory excitation device.Frequency range is 0 to 5,000 Hz.Now, absorb by means of power/acceleration, directly
Connect via reluctance head, measure the response of the glass specimen vibration to producing at different temperatures, and use analysis software (PULSE
FFT Analysis 7770N2 type/Br ü el & Kjaer GmbH) it is evaluated.By the conversion letter of the power measured and acceleration
Number, determines the different natural frequency of vibration mode n of glass specimenAnd half breadth.3dB under signal maximum
Place selects half breadth.Use formulaDetermine the loss factor under different natural frequenciesOr damping.High
Loss factor or high damping percentage ratio can serve as the quality metrics of sound insulation value.At the temperature model considered of 0 to 40 DEG C
Damping curve the widest in enclosing is valuable.
Because the damping capacity of material depends on temperature, so measuring this sample in the selected temperature scope at 5 DEG C of intervals,
Described temperature range covers the range of application of sound-absorbing glass in principle.
The measurement of the tensile property of film
According to ISO 527, with the speed of 200 mm/min, measure the tear of film by means of tester for elongation (TIRA company)
Intensity and the value of elongation at break.
Embodiment
1) the general synthesis step of polyvinyl alcohol contracting (just) aldehyde
The polyvinyl alcohol Mowiol 28-99 (from the commodity of Kuraray Europe GmbH) of 100 weight portions is dissolved in
In the water of 975 weight portions, it is simultaneously heated to 90 DEG C.The hutanal of 57.5 weight portions is added, the temperature of 12 DEG C the temperature of 40 DEG C
Degree under agitation adds 20% hydrochloric acid of 75 weight portions.73 are heated the mixture to after polyvinyl butyral resin (PVB) precipitates
DEG C, and stirring 2 hours at such a temperature.After cooling to room temperature, separate PVB, be washed with water to neutrality, and be dried.Obtain
There is the polyvinyl alcohol content of 20.3 weight % and the PVB of the polyvinyl acetate contents of 0.9 weight %.
2) there is the synthesis step of polyvinyl alcohol contracting (just) aldehyde of the polyvinyl alcohol content of 14.1 weight %
By the polyvinyl alcohol Mowiol 30-92 of 100 weight portions (from the commodity of Kuraray Europe GmbH, averagely
The degree of polymerization is 2100) it is dissolved in the water of 975 weight portions, it is simultaneously heated to 90 DEG C.56.8 weight portions are added the temperature of 40 DEG C
The glutaraldehyde b of hutanal and 0.06 weight portion, and 20% hydrochloric acid of 100 weight portions is under agitation added the temperature of 12 DEG C.Poly-
69 DEG C are heated the mixture to after vinyl butyral (PVB) precipitation, and stirring two hours at such a temperature.It is being cooled to room
After using warming therapy, separate PVB, be washed with water to neutrality, and be dried.Obtain polyvinyl alcohol content and 8.8 weights with 14.1 weight %
The PVB of the polyvinyl acetate contents of amount %.
3) there is the synthesis step of polyvinyl alcohol contracting (just) aldehyde of the polyvinyl alcohol content of 15.1 weight %
By the polyvinyl alcohol Mowiol 30-92 of 100 weight portions (from the commodity of Kuraray Europe GmbH, averagely
The degree of polymerization is 2100) it is dissolved in the water of 975 weight portions, it is simultaneously heated to 90 DEG C.55.5 weight portions are added the temperature of 40 DEG C
The glutaraldehyde b of hutanal and 0.06 weight portion, and 20% hydrochloric acid of 100 weight portions is under agitation added the temperature of 12 DEG C.Poly-
69 DEG C are heated the mixture to after vinyl butyral (PVB) precipitation, and stirring two hours at such a temperature.It is being cooled to room
After using warming therapy, separate PVB, be washed with water to neutrality, and be dried.Obtain polyvinyl alcohol content and 8.5 weights with 15.1 weight %
The PVB of the polyvinyl acetate contents of amount %.
4) there is the synthesis step of polyvinyl alcohol contracting (different) aldehyde of the polyvinyl alcohol content of 14.4 weight %
The polyvinyl alcohol Mowiol 30-92 (from the commodity of Kuraray Europe GmbH) of 100 weight portions is dissolved in
In the water of 975 weight portions, it is simultaneously heated to 90 DEG C.Isobutylaldehyde and 0.06 weight portion of 68.6 weight portions is added the temperature of 40 DEG C
Glutaraldehyde, and under agitation add 20% hydrochloric acid of 100 weight portions the temperature of 12 DEG C.At polyvinyl butyral resin (PVB)
69 DEG C are heated the mixture to after precipitation, and stirring 2 hours at such a temperature.After cooling to room temperature, separate PVB, use
Water washing is to neutral, and is dried.The polyvinyl acetate obtaining the polyvinyl alcohol content and 8.7 weight % with 14.4 weight % contains
The PVB of amount.
5) there is the synthesis step of polyvinyl alcohol contracting (different) aldehyde of the polyvinyl alcohol content of 15.6 weight %
The polyvinyl alcohol Mowiol 30-92 (from the commodity of Kuraray Europe GmbH) of 100 weight portions is dissolved in
In the water of 975 weight portions, it is simultaneously heated to 90 DEG C.Isobutylaldehyde and 0.06 weight portion of 67.6 weight portions is added the temperature of 40 DEG C
Glutaraldehyde, and under agitation add 20% hydrochloric acid of 100 weight portions the temperature of 12 DEG C.Sink at polyvinyl butyral resin (PVB)
69 DEG C are heated the mixture to after shallow lake, and stirring two hours at such a temperature.After cooling to room temperature, separate PVB, use water
Washing is to neutral, and is dried.Obtain polyvinyl alcohol content and the polyvinyl acetate contents of 8.6 weight % with 15.6 weight %
PVB.
6) there is the synthesis step of polyvinyl alcohol contracting (different) aldehyde of the polyvinyl alcohol content of 16.4 weight %
The polyvinyl alcohol Mowiol 30-92 (from the commodity of Kuraray Europe GmbH) of 100 weight portions is dissolved in
In the water of 975 weight portions, it is simultaneously heated to 90 DEG C.Isobutylaldehyde and 0.06 weight portion of 66.6 weight portions is added the temperature of 40 DEG C
Glutaraldehyde, and under agitation add 20% hydrochloric acid of 100 weight portions the temperature of 12 DEG C.Sink at polyvinyl butyral resin (PVB)
69 DEG C are heated the mixture to after shallow lake, and stirring two hours at such a temperature.After cooling to room temperature, separate PVB, use water
Washing is to neutral, and is dried.Obtain polyvinyl alcohol content and the polyvinyl acetate contents of 8.5 weight % with 16.4 weight %
PVB.
7) there is the synthesis step of polyvinyl alcohol contracting (different) aldehyde of the polyvinyl alcohol content of 17.9 weight %
The polyvinyl alcohol Mowiol 30-92 (from the commodity of Kuraray Europe GmbH) of 100 weight portions is dissolved in
In the water of 975 weight portions, it is simultaneously heated to 90 DEG C.Isobutylaldehyde and 0.06 weight portion of 60.8 weight portions is added the temperature of 40 DEG C
Glutaraldehyde, and under agitation add 20% hydrochloric acid of 100 weight portions the temperature of 12 DEG C.At polyvinyl butyral resin (PVB)
69 DEG C are heated the mixture to after precipitation, and stirring two hours at such a temperature.After cooling to room temperature, separate PVB, use
Water washing is to neutral, and is dried.The polyvinyl acetate obtaining the polyvinyl alcohol content and 8.6 weight % with 17.9 weight % contains
The PVB of amount.
The manufacture of film
By combining, manufacture by the film formed according to the sublayer formed of table 1.3G8 (2,2'-ethylenedioxybis(ethanol) .) is used as plasticising
Agent.
The film of embodiment 1 to the 4 display present invention, its have polyvinyl alcohol contracting (just) butyraldehyde/polyvinyl alcohol contracting (different) butyraldehyde/
Polyvinyl alcohol contracting (just) butyraldehyde structure, has identical polyvinyl alcohol in outer layer in every case and polyvinyl acetate contains
Amount.
Comparative example 1 and 2 display the film of non-invention, it has polyvinyl alcohol contracting (just) butyraldehyde/polyvinyl alcohol contracting (just)
Butyraldehyde/polyvinyl alcohol contracting (just) butyraldehyde structure, has, for internal layer and outer layer, the polyvinyl alcohol provided and polyvinyl acetate contains
Amount.
Table 2 shows the physical data about film.Its display is compared with the comparative example with the PVA content that may compare, originally
The film of invention has preferably damping at 20 DEG C.The PVA content of the Pioloform, polyvinyl acetal used is certainly for the damping capacity of film
Qualitatively.Compared with the film with low PVA content, based on identical MW content, there is the film of high PVA content to fixed temperature
Poor damping is generally shown under (being 20 DEG C in this case).But in embodiment 3 and 4, contain even having high PVA
Amount, the film of the present invention still shows good damping capacity at 20 DEG C.This point is the plasticizer phase due to inventive film
Capacitive improve, damping maximum can towards lower temperature elapse the fact.Higher plasticizer absorption generally means that the machine of film
Tool performance, such as tearing strength are impaired.But, it has now been found that compared with the comparative example 1 and 2 with similar PVA content, implement
The film of the present invention in example 1 and 2 has even preferably tearing strength.
。
Claims (8)
1. film laminates, is become with C-shaped by least three layer A, B, and each layer comprises at least one plasticizer and at least one polyethylene
Acetal, it is characterised in that
-two outer layer A with C comprise the most identical of at least one PVA-based ratio with 18.5 to 23 weight % or not
Same Pioloform, polyvinyl acetal
-at least one inner layer B comprises the Pioloform, polyvinyl acetal of the PVA-based ratio with 12 to 18 weight %, and
At least one of-layer A, B or C comprises at least one polyvinyl alcohol contracting (different) aldehyde,
Two of which outer layer A, C comprise at least one the most identical or different polyvinyl alcohol contracting (different) aldehyde, and inner layer B comprise to
Few a kind of polyvinyl alcohol contracting (just) aldehyde, or
Two outer layers A, C comprise at least one the most identical or different polyvinyl alcohol contracting (just) aldehyde, and inner layer B comprises at least one
Plant polyvinyl alcohol contracting (different) aldehyde, or
Two outer layers A, C comprise at least one the most identical or different polyvinyl alcohol contracting (different) aldehyde, and inner layer B comprises at least one
Plant polyvinyl alcohol contracting (different) aldehyde being different from layer A and C.
Film laminates the most according to claim 1, it is characterised in that at least one layer of A, B or C comprise at least one polyvinyl alcohol
Contracting (just) aldehyde.
3. according to the film laminates of one of claim 1 to 2, it is characterised in that by make at least one polyvinyl alcohol with a kind of or
Multiple comprise 4 to 10 carbon atoms and there is at the α position or β position of ketone group at least one branched aliphatic ketone compound reaction
Obtain polyvinyl alcohol contracting (different) aldehyde.
4. according to the film laminates of one of claim 1 to 2, it is characterised in that by make at least one polyvinyl alcohol with a kind of or
The multiple aliphatic nonbranched ketonic compound reaction comprising 2 to 10 carbon atoms obtains polyvinyl alcohol contracting (just) aldehyde.
5. according to the film laminates of one of claim 1 to 2, it is characterised in that according to the state by July 16th, 2002
ISO/PAS 16940, the temperature range of 17.5 to 22.5 DEG C, with this film laminates manufacture by 2 mm glass/0.8 mm films
The sample that layered product/2 mm glass is formed has the first mode damping value more than 19%.
6. according to the film laminates of one of claim 1 to 2, it is characterised in that manufacture film laminates by each layer of coextrusion.
7. according to the film laminates of one of claim 1 to 2, it is characterised in that manufacture film laminates by combining each layer.
8. it is used for automobile, aircraft, boats and ships, architectural glazings according to the film laminates of one of claim 1 to 7 for manufacture, stands
Glass film layered product/the glass composite of face component, or for manufacturing the purposes of photovoltaic module.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11175084.0 | 2011-07-22 | ||
| EP20110175084 EP2548728A1 (en) | 2011-07-22 | 2011-07-22 | Film laminates with damping characteristics containing a sub-layer of polyvinyl(iso)acetal containing plasticizers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102886952A CN102886952A (en) | 2013-01-23 |
| CN102886952B true CN102886952B (en) | 2016-11-30 |
Family
ID=
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2328646A (en) * | 1940-03-02 | 1943-09-07 | Du Pont | Polyvinyl butyral sheet material |
| US5190826A (en) * | 1990-05-14 | 1993-03-02 | Sekisui Chemical Co., Ltd. | Interlayers for use in sound-insulating laminated glasses |
| JPH0797240A (en) * | 1993-09-28 | 1995-04-11 | Sekisui Chem Co Ltd | Interlayer for laminated glass |
| CN101137501A (en) * | 2005-03-17 | 2008-03-05 | 索罗蒂亚公司 | Sound reducing polymer interlayers |
| CN101637991A (en) * | 2008-08-01 | 2010-02-03 | 可乐丽欧洲有限责任公司 | Multilayer films of plasticizer-containing polyvinyl acetal with sound-absorbing properties |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2328646A (en) * | 1940-03-02 | 1943-09-07 | Du Pont | Polyvinyl butyral sheet material |
| US5190826A (en) * | 1990-05-14 | 1993-03-02 | Sekisui Chemical Co., Ltd. | Interlayers for use in sound-insulating laminated glasses |
| JPH0797240A (en) * | 1993-09-28 | 1995-04-11 | Sekisui Chem Co Ltd | Interlayer for laminated glass |
| CN101137501A (en) * | 2005-03-17 | 2008-03-05 | 索罗蒂亚公司 | Sound reducing polymer interlayers |
| CN101637991A (en) * | 2008-08-01 | 2010-02-03 | 可乐丽欧洲有限责任公司 | Multilayer films of plasticizer-containing polyvinyl acetal with sound-absorbing properties |
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