CN102892822A - 具有3-叔丁基-4-羟基-5-甲基苯基丙酸酯部分结构的酚类抗氧化剂的pvb薄膜 - Google Patents
具有3-叔丁基-4-羟基-5-甲基苯基丙酸酯部分结构的酚类抗氧化剂的pvb薄膜 Download PDFInfo
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- CN102892822A CN102892822A CN2011800238122A CN201180023812A CN102892822A CN 102892822 A CN102892822 A CN 102892822A CN 2011800238122 A CN2011800238122 A CN 2011800238122A CN 201180023812 A CN201180023812 A CN 201180023812A CN 102892822 A CN102892822 A CN 102892822A
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- -1 3-t-butyl-4-hydroxy-5-methylphenyl Chemical group 0.000 title description 17
- 239000002530 phenolic antioxidant Substances 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 43
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- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
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- 239000011521 glass Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001838 alkalimetric titration Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 3
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
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- ZWYAVGUHWPLBGT-UHFFFAOYSA-N bis(6-methylheptyl) decanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCCCCCC(=O)OCCCCCC(C)C ZWYAVGUHWPLBGT-UHFFFAOYSA-N 0.000 description 4
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- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 3
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- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 2
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000005041 acyloxyalkyl group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 description 2
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- 239000004806 diisononylester Substances 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
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- 150000002989 phenols Chemical class 0.000 description 2
- 150000003016 phosphoric acids Chemical class 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
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WTTWSMJHJFNCQB-UHFFFAOYSA-N 2-(dibenzylamino)ethanol Chemical compound C=1C=CC=CC=1CN(CCO)CC1=CC=CC=C1 WTTWSMJHJFNCQB-UHFFFAOYSA-N 0.000 description 1
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Natural products CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 1
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- IHLDEDLAZNFOJB-UHFFFAOYSA-N 6-octoxy-6-oxohexanoic acid Chemical compound CCCCCCCCOC(=O)CCCCC(O)=O IHLDEDLAZNFOJB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 101100489867 Mus musculus Got2 gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 229960000250 adipic acid Drugs 0.000 description 1
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- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
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- 230000008033 biological extinction Effects 0.000 description 1
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- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 1
- 244000240602 cacao Species 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 102220007331 rs111033633 Human genes 0.000 description 1
- 102220029346 rs34541442 Human genes 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10678—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising UV absorbers or stabilizers, e.g. antioxidants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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Abstract
本发明涉及热塑性混合物或由此挤出的薄膜,所述热塑性混合物包含至少一种聚乙烯醇缩醛和至少一种增塑剂,其特征在于,添加0.001到1重量%的至少一种式1的化合物作为稳定剂,其中R=多元醇的烃基、具有1至10个二醇单元的寡聚二醇或具有1至20个碳原子的烃残基,和X=1、2、3或4。
Description
技术领域
本发明涉及含有增塑剂的聚乙烯醇缩醛的混合物或由此挤出的薄膜,通过使用特别合适的酚类抗氧化剂使其具有少的固有颜色和高的光热稳定性。
技术背景
像许多其他的热塑性塑料一样,聚乙烯醇缩丁醛经常配备有酚类抗氧化剂(酚类AO),它们的任务是,例如,在薄膜挤出时抑制由高加工温度引起的自由基裂解反应。由此使聚合物链的长度基本上保持恒定,从而使挤出的材料的机械性能不会由于挤出过程而变差。
然而许多酚类抗氧化剂带来的缺点是,根据挤出的条件会引起黄变,这归因于抗氧化剂的反应产物。甚至在制成的、已经粘合在两个玻璃板之间的PVB薄膜中,酚类抗氧化剂也会在紫外线辐射下,特别是在升高的温度下,导致后来变黄,这不仅出于美观的原因是不希望的,而且玻璃层压板的透光率也会随时间而降低。
例如,在WO 03/078160 A1(Du Pont)中优选用于含有增塑剂3G8的PVB薄膜的双环酚类抗氧化剂,例如Lowinox 44B25及22M46,在紫外线辐射下表现为比较强地发黄。
某些抗氧化剂,例如BHT(CAS登记号:128-37-0),虽然是紫外稳定的,但是由于其分子量小而较易挥发,因此在没有被玻璃覆盖的薄膜材料中沿着层压板的边缘会发生抗氧化剂提早耗尽并且无法较长时间地保护在薄膜的这些位置上的聚合物链免受链降解。此外,BHT具有的缺点是,在温度升高和遇到氧气时会产生带有鲜黄色的反应产物。在作为复合安全玻璃或光伏模块的应用中,这可以以这样的形式显现出缺陷,即在压热器法或稳定性测试后在层压板的边缘区域出现PVB薄膜变黄。
目的
本发明的目的在于,鉴定出专门适合于在通过挤出制备含有增塑剂的聚乙烯醇缩醛薄膜时的高要求的酚类抗氧化剂,该酚类抗氧化剂可用于光学上的应用,即表现为在层压的薄膜上无边缘黄变,在挤出中无不可接受的黄色值的增加以及特别良好的光热稳定性。
目的的解决方案
令人惊讶地已发现,通过使用具有3-叔丁基-4-羟基-5-甲基苯基丙酸酯单元作为部分结构的酚类抗氧化剂,可以得到具有少的固有颜色和特别高的光热稳定性的含增塑剂的聚乙烯醇缩醛的薄膜。
因此,本发明的主题是热塑性混合物,其含有至少一种聚乙烯醇缩醛和至少一种增塑剂或由其制备的薄膜,其特征在于,添加0.001到1重量%的至少一种式1的化合物作为稳定剂,
其中R=多官能醇的烃基,具有1至10个二醇单元的寡聚二醇或具有1至20个碳原子的烃残基,以及X=1、2、3或4。
合适的式1的稳定剂例如式1a的那些
其中n=1到10或式1b的那些
本发明的另一个主题是,根据式1、1a或1b的化合物作为用于由至少一种增塑剂和至少一种聚乙烯醇缩醛组成的热塑性混合物的稳定剂的应用。
根据式1、1a或1b的合适的稳定剂是CAS登记号36443-68-2的那些,它们例如可可从CIBA公司作为IRGANOX 245,从CHEMTURA公司作为Lowinox GP45或从SONGWON公司作为Songnox2450获得,以及是CAS登记号90498-90-1的那些,可从Sumimoto公司以名称SUMILIZER GA80获得。
根据本发明的混合物或薄膜中优选含有0.005-0.5重量%,特别优选0.01-0.25重量%,特别是0.02-0.1重量%,并且最优选0.03-0.08重量%的根据式1的具有部分结构3-叔丁基-4-羟基-5-甲基苯基丙酸酯的酚类抗氧化剂。
除了使用根据式1、1a或1b的稳定剂,根据本发明的混合物低的碱滴定度的设定,例如在聚乙烯醇缩醛的中和时,可导致根据本发明的混合物或薄膜的固有颜色和光热稳定性的改善。
如实施例中所示的,所述碱滴定度通过用盐酸中和根据本发明的混合物或薄膜来确定,并优选在2和70之间,特别在3至50之间和最优选在5至30之间。
碱滴定度的设定可以在通过聚乙烯醇的缩醛化来生产聚乙烯醇缩醛的期间或之后通过聚乙烯醇缩醛的相应中和,或者通过向根据本发明的混合物中添加金属盐来实现。所述金属盐在根据本发明的薄膜用于复合玻璃层压板时通常也作为防粘连剂起作用。
特别适合于根据本发明的混合物的是聚乙烯醇缩醛,它可作为聚乙烯醇PVA与丁醛的缩醛化产物,即聚乙烯醇缩丁醛(PVB)得到。根据本发明的混合物可以含有一种或多种聚乙烯醇缩醛,其可以在分子量、缩醛化程度、残余醇含量或缩醛基团的性质方面有所不同。
根据本发明的混合物或薄膜可含有作为防粘连剂的碱土金属离子、锌离子、铝离子以及碱金属离子。它们以一价或多价的无机酸或者一元或多元的有机酸的盐的形式存在于该混合物/薄膜中。抗衡离子的例子例如是有机羧酸的盐,例如甲酸盐、乙酸盐、三氟乙酸盐、丙酸盐、丁酸盐、苯甲酸盐、2-乙基己酸盐等,其中优选使用具有少于10个碳原子,优选少于8个,优选少于6个,优选少于4个和特别优选具有少于3个碳原子的羧酸。无机抗衡离子的例子为氯化物、硝酸盐、硫酸盐、磷酸盐。其它的抗衡离子可以是算作表面活性剂的阴离子,例如磺酸盐或磷酸酯型的表面活性剂。
此外,所提及的根据本发明的混合物的良好光学性能可以通过选择用来生产聚乙烯醇缩醛的聚乙烯醇(PVA)来改善。如果在PVA阶段,聚合物链中的不饱和单元作为缺陷位存在,则这些也不可避免地再次出现在由此制造的聚乙烯醇缩醛中,由此增加了其吸收的紫外线辐射并且恶化了光稳定性。所述不饱和单元可以以独立的或彼此共轭的或者与羰基化合物共轭的双键的形式存在。这些不饱和单元可以通过PVA中的紫外光谱被检测到。
非常高的缺陷位的比例导致在4重量%的水溶液中测量所用的PVA时,在280nm处的消光接近1。因此,为了制备根据本发明使用的聚乙烯醇缩醛,优选使用聚乙烯醇,它在4重量%的水溶液中在280nm处具有小于0.5,小于0.3,特别是0.2和优选0.1的消光值。
由于它良好的光热自身稳定性,苯并三唑类的化合物,特别是Tinuvin 328、327和326型适合作为紫外吸收剂。根据本发明明确包括苯并三唑类的应用。虽然由此制作的薄膜具有更高的固有颜色,但是在辐照测试后也具有特别低的Δb*值。
同样除了使用根据式1的带有部分结构3-叔丁基-4-羟基-5-甲基苯基丙酸酯的酚类抗氧化剂外,以及代替或除了上述挥发性的抗氧化剂,根据本发明的混合物或薄膜可以配备有一种或多种非芳族的光稳定剂,特别是0.001到1重量%(基于该薄膜混合物计)的空间位阻的HAS/HALS/NOR-HALS型的胺(空间位阻的氨基醚),从而能够获得光热稳定性的进一步改善。
特别适合的非芳族的光稳定剂为空间位阻的通式II、III和或IV的胺。
其中R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11=非芳香取代基,如H、C1-C20烷基、羟基烷基、烷氧基烷基、酰氧基烷基,在每种情况下未取代或被醛基、酮基或环氧基取代
R12=直接键(glatte Verbindung)、C1-C20烷基、羟基烷基、烷氧基烷基、酰氧基烷基,在每种情况下未取代或被醛基、酮基或环氧基取代
n=2-4
m=1-10。
这种类型的化合物是市售可得的,合适的例如是Ciba Specialities公司的Tinuvin 123(NOR-HALS)、Tinuvin 144、Tinuvin 622、Tinuvin 770及其二-N-甲基化的衍生物。尤其非常合适的是Asahi Denka Co.公司的ADK Stab LA-57、LA-52或LA-62或BASF AG的UVINUL 4050H。
除了使用根据式1的具有部分结构3-叔丁基-4-羟基-5-甲基苯基丙酸酯的酚类抗氧化剂,所述热塑性混合物/薄膜可以含有用其它的光稳定的、由于另外的性质,例如高的挥发性而不太适合单独使用的酚类抗氧化剂进行的基本稳定。因此,在本发明范围内,抗氧化剂意指在PVB薄膜的挤出条件和加工条件下具有提高的挥发性的抗氧化剂,其通常针对具有小于300g/mol的分子量的酚类抗氧化剂。这些另外的酚类抗氧化剂可以用来代替或与上述HAS/HALS/NOR-HALS型空间位阻胺结合使用。优选地,根据本发明的热塑性混合物或薄膜含有0.001-0.25重量%(基于薄膜混合物计)的具有分子量小于300g/mol的酚类抗氧化剂。特别合适的酚类抗氧化剂是BHT(CAS登记号128-37-0)或4-叔辛基苯酚(CAS登记号140-66-9)。
具有部分结构3-叔丁基-4-羟基-5-甲基苯基丙酸酯的式1的空间位阻酚类抗氧化剂,以及任选另外的抗氧化剂,可以通过不同方式引入到根据本发明的混合物或由其生产的薄膜中。可以使它们在挤出前已经包含于聚合物中,或在挤出过程中或在共混制备阶段中溶解或悬浮在增塑剂中来添加。优选地,已将酚类抗氧化剂在PVB的合成阶段,例如通过喷洒到成品聚合物颗粒上或在PVB-聚合物从反应溶液中析出的过程中引入。这同样适用于空间位阻胺的光稳定剂的添加,其中优选将其溶解在增塑剂中添加。
优选地,该薄膜具有5-45重量%,12-36重量%,14-32重量%,16-30重量%,特别是20-28重量%的总增塑剂含量,即薄膜中所有增塑剂的比例。根据本发明的薄膜或由其粘接的层压板可以含有一种或多种增塑剂。
用于根据本发明的混合物或薄膜的基本上合适的增塑剂是选自下列组中的一种或多种化合物:
多元的脂族或芳族酸的酯,例如己二酸二烷基酯,如己二酸二己酯、己二酸二辛酯、己二酸己基环己酯、己二酸庚酯和己二酸壬酯的混合物、己二酸二异壬基酯、己二酸庚基壬酯以及己二酸与脂环族或含醚键的酯醇的酯,癸二酸二烷基酯,如癸二酸二丁酯以及癸二酸与脂环族或含醚键的酯醇的酯,邻苯二甲酸的酯,如邻苯二甲酸丁基苄酯或双-2-丁氧基乙基邻苯二甲酸酯。
带有一个或多个非支链的或支链的脂族或芳族取代基的脂族或芳族多元醇或低聚醚二醇的酯或醚,如二-、三-或四甘醇与直链或支链的脂族或脂环族羧酸的酯;
下述物质可以用作后一组的例子
二甘醇-双-(2-乙基己酸酯)、三甘醇-双-(2-乙基己酸酯)、三甘醇-双-(2-乙基丁酸酯)、四甘醇-双-正庚酸酯、三甘醇-双-正庚酸酯、三甘醇-双-正己酸酯、四甘醇二甲基醚和/或二丙二醇苯甲酸酯
脂族或芳族酯醇的磷酸盐,例如三(2-乙基己基)磷酸酯(TOF)、磷酸三乙酯、二苯基-2-乙基己基磷酸酯、和/或磷酸三甲苯酯
柠檬酸、琥珀酸和/或富马酸的酯,
非常合适作为增塑剂用于根据本发明的混合物或薄膜的是选自下列的一种或多种化合物:
癸二酸二-2-乙基己酯(DOS)、己二酸二-2-乙基己酯(DOA)、己二酸二己酯(DHA)、癸二酸二丁酯(DBS)、己二酸二异壬酯(DINA)、三甘醇-双-正庚酸酯(3G7)、四甘醇-双-正庚酸酯(4G7)、三甘醇-双-2-乙基己酸酯(3GO或3G8)、四甘醇-双-正-2-乙基己酸酯(4GO或4G8)、己二酸二-2-丁氧基乙酯(DBEA)、己二酸二-2-丁氧基乙氧基乙酯(DBEEA)、癸二酸二-2-丁氧基乙酯(DBES)、邻苯二甲酸二-2-乙基己酯(DOP)、邻苯二甲酸二异壬酯(DINP)、三甘醇-双-异壬酸酯、三甘醇-双-2-丙基己酸酯、三(2-乙基己基)磷酸酯(TOF)、1,2-环己烷二羧酸二异壬酯(DINCH)和二丙二醇苯甲酸酯。
最特别合适的是,其由式100x O/(C+H)表达的极性小于/等于9.4的增塑剂,其中O、C和H表示在每个分子中氧原子、碳原子和氢原子的数目。下面的表格显示了根据本发明可以使用的增塑剂及它们的根据式100x O/(C+H)的极性值。
表1
名称 | 缩写 | 100x O/(C+H) |
癸二酸二-2-乙基己酯 | DOS | 5.3 |
己二酸二异壬酯 | DINA | 5.3 |
1,2-环己烷二羧酸二异壬酯 | DINCH | 5.4 |
己二酸二-2-乙基己酯 | DOA | 6.3 |
己二酸二己酯 | DHA | 707 |
癸二酸二丁酯 | DBS | 7.7 |
三甘醇-双-2-丙基己酸酯 | 8.6 | |
三甘醇-双-异壬酸酯 | 8.6 | |
癸二酸二-2-丁氧基乙酯 | DBES | 9.4 |
三甘醇-双-2-乙基己酸酯 | 3G8 | 9.4 |
此外,根据本发明的混合物或薄膜可以另外含有其它的添加剂,例如抗静电剂、填料、IR吸收纳米颗粒或发色团、染料、表面活性物质、螯合剂、含环氧基团的化合物、颜料以及粘附调节剂。
基于聚乙烯醇缩醛的薄膜的原则上的生产和组成描述在例如EP185863B1,EP1118258B1WO02/102591A1,EP1118258B1或EP387148B1中。
根据本发明的热塑性混合物可以以常规的方式在约160到230℃被挤出成薄膜。这样的薄膜优选具有小于5,特别优选小于4,和特别小于3和Δb*值小于3,优选小于2.5,特别优选小于2和尤其是小于1.5的DYI。
根据本发明的薄膜可用于制备复合玻璃层压板、挡风玻璃或光伏模块。
测试和测量方法:
薄膜的照射稳定性在复合玻璃中在两片厚度为2毫米的Optiwhite型玻璃(Pilkington公司的贫氧化铁玻璃与典型的透明玻璃相比,具有增加的对UV-A辐射的通透性)之间测试。在这里,将具有尺寸15×15厘米的层压板置于根据EN12543的照射室中20周的时间。与EN12543的条件不同,设定了更高的恒定为80℃的样品温度,因为该条件更符合在应用中在不利情况下实际发生的组合的辐射负荷和温度负荷。
通过比较测量经照射的层压板与暗处储藏的原始层压板的b*值(CIELab),可以容易地确定b*值的相对增加作为具有各稳定剂类型或各稳定剂组合的PVB薄膜的辐射稳定性的度量。b*值的测量在制造商Hunterlab的颜色测量仪“ColorQuest XE”上使用CIELAb-系统在透射(10°/D65)中进行。Δb*值表示经照射的样品的b*值和原始样品的b*值的之间的差。
为了更好地区分挤出薄膜的固有颜色(无额外的由辐照引起的负荷),将具有10层厚度为0.76毫米的薄膜(即总膜厚度是7.6毫米)与2片透明玻璃(2毫米Planilux)的复合玻璃在ColorQuest XE上根据以下方法测量。在此方法中,该玻璃的固有颜色通过测量作为空白样品的相同玻璃批次的一对玻璃标定。黄度指数(YI[01925])的计算根据条件Hunterlab 2°/光类型C自动进行。DYI值是YI(层压板10×0.76)-YI(玻璃对)的差。
热氧化稳定性(边缘稳定性)在尺寸为15×15厘米的浮法玻璃上取2×3毫米的测试层压板上评估。在常规的辊压预复合步骤之后,测试层压板将经历一个漫长和热的高压釜过程,以制备最终复合体,所述高压釜过程在总时间为6小时情况下包括在160℃和12巴下3小时的保持时间。作为热氧化负荷的结果,和作为选择的稳定化变量的函数,在这里位于测试层压板边缘的薄膜物料(Masse)在从“完全无色”到“深琥珀色”的带宽内变色。前者被归为0分,后者为6分,中间的相应分级分配。
聚乙烯醇缩醛的聚乙烯醇含量和聚乙烯醇乙酸酯的含量根据ASTMD 1396-92来测定。金属离子含量的分析通过原子吸收光谱仪(AAS)来进行。薄膜的水含量或湿含量由卡尔-费歇尔(Karl-Fischer)法测定。
为了确定缩醛化中使用的聚乙烯醇的UV吸收,在UV/VIS光谱仪,例如Perkin-Elmer Lambda 910中,将其作为4%的水溶液以1厘米的层厚度在280nm波长处测量。在这里,测量值基于PVA的干物质含量。
为了确定碱滴定度,将3到4克含有增塑剂的聚乙烯醇缩醛薄膜在乙醇/四氢呋喃(80∶20)的100毫升混合物中用电磁搅拌器过夜溶解。为此加入10毫升稀盐酸(c=0.01摩尔/升),然后用氢氧化四丁基铵(TBAH)的2-丙醇溶液(c=0.01摩尔/升)用Titroprozessor相对于空白样品进行电位滴定。如下进行碱滴定度的计算:
碱滴定度=ml盐酸/100克样品=(消耗的TBAH空白样品-TBAH试样x 100/以克计的试样重量)。
实施例
将下表中给出的混合物在物料通过量为85千克/小时的挤出机上和在物料温度为200℃下挤出得到厚度为0.76毫米的薄膜。除非另有说明,所有的值均基于薄膜混合物计以重量%给出。
除了根据本发明的稳定剂以外,实施例2、4和7的组成还具有分子量小于300g/mol的抗氧化剂;实施例5还展示了一种HALS稳定剂。
对比例1和2仅具有常用的稳定剂且没有根据本发明的具有式1、1a或1b的部分结构的稳定剂。除了明显变差的热氧化稳定性(对比例1)以外,薄膜显示了不可接受的变色,其通过Δb*和DYI的值来表明。
表2
表3
表4
Claims (14)
1.热塑性混合物,其含有至少一种聚乙烯醇缩醛和至少一种增塑剂,其特征在于,添加0.001到1重量%的至少一种式1的化合物
3.其中R=多元醇的烃基、双官能的环醚、双官能团的环二醚、双官能的二噁烷衍生物、具有1至10个二醇单元的寡聚二醇或具有1至20个碳原子的烃残基,和X=1、2、3或4,作为稳定剂。
6.根据权利要求1的热塑性混合物,其特征在于,使用CAS登记号36443-68-2或CAS登记号90498-90-1的那些作为式1的稳定剂。
7.根据权利要求1到4之一的热塑性混合物,其特征在于,所述混合物具有2-70的碱滴定度。
8.根据权利要求1到5之一的热塑性混合物,其特征在于,所述混合物另外含有0.001-1重量%的HAS/HALS/NOR-HALS型非芳香族的光稳定剂。
9.根据权利要求1到6之一的热塑性混合物,其特征在于,所述混合物另外含有0.001-0.25重量%的具有小于300g/mol的分子量的酚类抗氧化剂。
10.由根据权利要求1到7的热塑性混合物制成的薄膜。
11.根据权利要求8的薄膜,其特征在于,该薄膜具有小于3的Δb*值。
12.根据权利要求9的薄膜,其特征在于,该薄膜具有小于5的固有颜色DYI。
13.根据权利要求8到10的薄膜用于生产复合玻璃、挡风玻璃或光伏模块的用途。
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CN108884326A (zh) * | 2016-03-28 | 2018-11-23 | 积水化学工业株式会社 | 热塑性树脂膜以及含有玻璃板的叠层体 |
CN111533832A (zh) * | 2020-04-09 | 2020-08-14 | 建滔(佛冈)特种树脂有限公司 | 一种耐黄变的聚乙烯醇缩丁醛树脂及其制备方法和应用 |
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US10293517B2 (en) * | 2015-08-30 | 2019-05-21 | Kuraray Europe Gmbh | Process for extrusion of plasticized PVB film with reduced plate-out of adhesion control agent residues |
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