JPWO2012133668A1 - ポリビニルアセタール系樹脂フィルムおよびそれを用いた多層構造体 - Google Patents
ポリビニルアセタール系樹脂フィルムおよびそれを用いた多層構造体 Download PDFInfo
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- JPWO2012133668A1 JPWO2012133668A1 JP2012538127A JP2012538127A JPWO2012133668A1 JP WO2012133668 A1 JPWO2012133668 A1 JP WO2012133668A1 JP 2012538127 A JP2012538127 A JP 2012538127A JP 2012538127 A JP2012538127 A JP 2012538127A JP WO2012133668 A1 JPWO2012133668 A1 JP WO2012133668A1
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- Prior art keywords
- film
- polyvinyl acetal
- shrinkage rate
- heat shrinkage
- width direction
- Prior art date
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- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 115
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000011354 acetal resin Substances 0.000 title claims description 77
- 229920006324 polyoxymethylene Polymers 0.000 title claims description 77
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- 239000005340 laminated glass Substances 0.000 claims abstract description 39
- -1 organic acid salt Chemical class 0.000 claims description 41
- 150000001241 acetals Chemical class 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
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- 239000011229 interlayer Substances 0.000 claims description 3
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- 238000009823 thermal lamination Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 238000011049 filling Methods 0.000 abstract description 4
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 1
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- 150000001299 aldehydes Chemical class 0.000 description 22
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- 238000003475 lamination Methods 0.000 description 13
- 239000000155 melt Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
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- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 7
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- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
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- 238000005259 measurement Methods 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
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- 229910010272 inorganic material Inorganic materials 0.000 description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 3
- 239000011654 magnesium acetate Substances 0.000 description 3
- 235000011285 magnesium acetate Nutrition 0.000 description 3
- 229940069446 magnesium acetate Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
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- 229910017604 nitric acid Inorganic materials 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
- 239000005341 toughened glass Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000007983 Tris buffer Substances 0.000 description 2
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- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
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- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
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- HRECPBLGWOTTIT-UHFFFAOYSA-N 3,9-bis(2-dodecylsulfanylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OC(CCSCCCCCCCCCCCC)OCC21COC(CCSCCCCCCCCCCCC)OC2 HRECPBLGWOTTIT-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
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- B29C48/001—Combinations of extrusion moulding with other shaping operations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
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- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
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- Extrusion Moulding Of Plastics Or The Like (AREA)
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Abstract
Description
攪拌機を取り付けた2m3反応器に、ポリビニルアルコール(以下、「PVA」と略記載することがある。)(PVA−1:重合度1700、ケン化度99モル%)7.5%の水溶液1700kgと、ブチルアルデヒド74.6kg、2,6−ジ−t−ブチル−4−メチルフェノール0.13kgを仕込み、全体を14℃に冷却した。これに、濃度20質量%の塩酸160.1Lを添加して、PVAのブチラール化を開始した。塩酸の添加が終了してから10分後より、90分かけて65℃まで昇温し、更に120分反応を行った。その後、室温まで冷却して析出した樹脂をろ過し、樹脂に対して10倍量(質量比)のイオン交換水で10回洗浄した。その後、0.3質量%水酸化ナトリウム水溶液を用いて充分に中和を行った。さらに、樹脂に対して10倍量(質量比)のイオン交換水で10回洗浄し、脱水したのち、乾燥させ、PVB樹脂(PVB−1)を得た。得られたPVB樹脂は、酢酸ビニル単位0.9モル%、ビニルアルコール単位28.5モル%であった。また、PVB樹脂の平均アセタール化度は70.6モル%であった。
実施例1のBF−1の中央部を中心にして幅51cm、長さ51cmのフィルムサンプルを得た(BF−4)。このフィルムの厚さ分布、揮発分、熱収縮率を実施例1と同様に測定した。厚さ分布の最大値は3%、揮発分は0.4質量%、熱収縮率は、熱収縮率MD1が6.4%、熱収縮率TD1が−0.9%、熱収縮率MD2が5.0%、熱収縮率TD2が−1.0%、熱収縮率MD3が7.6%、熱収縮率TD3が−0.3%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、0.24g/10分であった。このフィルムを用いた以外は、実施例1と同様に配し、合わせガラスを作製した。0.5mm以下の気泡がエッジ部に5箇所見られたが、PVBの欠損部分は無かった。
実施例1のBF−2を再度巻き出し、表面温度120℃の金属ロール(直径40cm)を通過させ、続いて表面温度120℃の金属製エンボスロール(直径40cm)と反対側に硬質ゴムロールを配し両ロールの間隙を0.7mmに調整した間を1m/分の速度で通過させ、フィルム表面に低辺1mm、高さ100μmの四角錘が連続するエンボス表面を持つフィルムロールを得た。エンボス後のフィルムの幅は51.3cmであった。このフィルムの厚さ分布の最大値は3%、揮発分は0.3質量%、熱収縮率は、熱収縮率MD1が10.2%、熱収縮率TD1が−2.0%、熱収縮率MD2が4.8%、熱収縮率TD2が−0.4%、熱収縮率MD3が5.2%、熱収縮率TD3が−0.9%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、0.23g/10分であった。このフィルムを長さ方向で51cmに切り出し、幅51.3cm×長さ51cmのサンプルフィルムとし、実施例1で使用した熱強化ガラスの中心と、フィルムの中心を合わせて重ね合わせ、以下実施例1と同様にして合わせガラスを得た。合わせガラスには気泡はなく、PVB欠損部分も見られなかった。
ペレット化の際に酢酸マグネシウムをPVB樹脂に対して質量基準で100ppm添加すること以外は実施例1と同様にしてペレットを得て、同様にして製膜しフィルム幅112cmのフィルムを得て(BF−5)、さらに実施例1と同様にスリッターにて51cm幅の2本のロール上に巻き取り、BF−6(正対して左)、BF−7(正対して右)とした。BF−6の厚さ分布の最大値は6%、揮発分は0.4質量%、熱収縮率は、熱収縮率MD1が13.8%、熱収縮率TD1が−4.1%、熱収縮率MD2が6.7%、熱収縮率TD2が−0.4%、熱収縮率MD3が7.6%、熱収縮率TD3が−1.1%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、0.10g/10分であった。以下、実施例1と同様にして合わせガラスを作製した。合わせガラスには気泡、PVB欠損部分は見られず外観良好であった。
実施例1において、製膜速度を0.3m/分になるよう吐出量を調整し、ダイリップとフィルムの第一ロールへの接触距離が3cmとして、以下は同様に製膜し、トリムカット前の幅87cmのフィルムを得た。両側をそれぞれ18cmトリムカットし、幅51cmのフィルムロールを得た(BF−8)。BF−8の厚さ分布の最大値は4%、揮発分は0.5質量%、熱収縮率は、熱収縮率MD1が2.1%、熱収縮率TD1が−0.1%、熱収縮率MD2が1.8%、熱収縮率TD2が0.0%、熱収縮率MD3が1.3%、熱収縮率TD3が−0.1%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、0.24g/10分であった。以下、実施例1と同様にして合わせガラスを作製した。合わせガラスにはエッジ部分に気泡が多数見られ、エッジ部から内側に向かってトンネル状に延びたPVB欠損部分が、元々ガラス間に空隙があった部分に多数見られた。
実施例1においてBF−2から51cm×51cmのフィルムを切り出し、10℃、70%RHで3日間保持した。フィルムの寸法変化は見られなかった。得られたフィルムの厚さ分布の最大値は5%、揮発分は1.4質量%、調湿後の熱収縮率は、熱収縮率MD1が26.2%、熱収縮率TD1が−5.9%、熱収縮率MD2が8.6%、熱収縮率TD2が−0.5%、熱収縮率MD3が10.1%、熱収縮率TD3−1.4%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、発泡し正確な測定は不能であった。これを用い、実施例1と同様に合わせガラスを作製した。中央部に多数の気泡が見られ、かつエッジ部分に多数の気泡とエッジから内部に向かってトンネル上のPVB欠損部分がほぼ全周に渡って観察された。
実施例1において製膜時に、同じ厚さで、製膜速度を2m/分となるよう吐出量を約3倍に調整して、ダイリップとフィルムの第一ロールへの接触距離を20cmとして、フィルムを得た(BF−9)。以下実施例1と同様にして、幅51cmのロールを2本得て、巻き取り方向に正対して左(BF−10)を用い、以下実施例1と同様な評価を行った。このフィルムの厚さ分布の最大値は6%、揮発分は0.4質量%、熱収縮率は、熱収縮率MD1が25.1%、熱収縮率TD1が−5.8%、熱収縮率MD2が7.9%、熱収縮率TD2が−4.3%、熱収縮率MD3が5.3%、熱収縮率TD3が−2.1%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、0.22g/10分であった。以下、実施例1と同様にして合わせガラスを作製した。合わせガラスにはエッジ部分に気泡が多数見られ、エッジ部から内側に向かってトンネル状に延びたPVB欠損部分が、元々ガラス間に空隙があった部分に多数見られた。
上述のようにして得られた実施例1〜4および比較例1〜3のポリビニルアセタール系樹脂フィルムの物性を表1に示す。
2 ガラス
3 ポリビニルアセタール系樹脂フィルム
4 トンネル状欠点
5 気泡
6 被積層体
7 押さえ用膜
8 大気圧
9 真空空間
10 真空ラミネーターのテーブル(または真空バッグ)
11 欠点頻出部
12 製品フィルム
13 サンプルA
14 サンプルB
15 サンプルC
Claims (13)
- 幅方向の厚さ分布が10%以下、揮発分が1.0質量%以下のフィルムであって、
幅方向の両端からフィルム全幅の5%内側部分について、それぞれ150℃で30分加熱した際に、フィルムに平行かつ幅方向に垂直である流れ方向の熱収縮率が大きい方の値を熱収縮率MD1、もう一方の値を熱収縮率MD2とし、
フィルムの幅方向の中央部分を150℃で30分加熱した際のフィルムに平行かつ幅方向に垂直である流れ方向の熱収縮率を熱収縮率MD3とした場合に、
熱収縮率MD1、熱収縮率MD2および熱収縮率MD3のいずれも3〜20%であるポリビニルアセタール系樹脂フィルム。 - 幅方向の両端から全幅の5%内側部分について、それぞれ150℃で30分加熱した際に、フィルムに平行かつ流れ方向に垂直である幅方向の熱収縮率を熱収縮率TD1および熱収縮率TD2とした場合に、熱収縮率TD1および熱収縮率TD2のいずれもが0%以下であって、
それぞれの幅方向の熱収縮率の絶対値が、同じ部分の流れ方向の熱収縮率の絶対値以下である請求項1に記載のポリビニルアセタール系樹脂フィルム。 - 熱ラミネート用である請求項1〜3のいずれか1項に記載のポリビニルアセタール系樹脂フィルム。
- フィルムの表面に高低差20μm以上のエンボスまたは連続した凹部を持つ、請求項1〜4のいずれか1項に記載のポリビニルアセタール系樹脂フィルム。
- さらに、2価以上の金属の有機酸塩をポリビニルアセタール系樹脂に対して、金属原子換算で1〜1000ppm含む請求項1〜5のいずれか1項に記載のポリビニルアセタール系樹脂フィルム。
- 請求項1〜6に記載のフィルムを押出機を用いて製膜するにあたり、ダイから押出す際のポリビニルアセタール系樹脂の温度が150〜250℃であり、ダイリップとダイリップから最も近いロールにおけるフィルムの接触地点との距離が5〜15cmであり、製膜速度が0.4〜20m/分である、ポリビニルアセタール系樹脂フィルムの製造方法。
- 請求項1〜6のいずれか1項に記載のポリビニルアセタール系樹脂フィルムを有する多層構造体。
- 上記ポリビニルアセタール系樹脂フィルムが少なくとも一方の表面にある、請求項8に記載の多層構造体。
- 請求項1〜6のいずれか1項に記載のポリビニルアセタール系樹脂フィルムを用いた太陽電池用封止材。
- 請求項10に記載の太陽電池用封止材を用いた太陽電池モジュール。
- 請求項1〜6のいずれか1項に記載のポリビニルアセタール系樹脂フィルムを用いた合わせガラス用中間膜。
- 請求項12に記載の合わせガラス用中間膜を用いた合わせガラス。
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JP4478990B2 (ja) * | 2007-09-21 | 2010-06-09 | ヤマトミシン製造株式会社 | ミシンの送油ポンプ装置 |
DE102007000816A1 (de) * | 2007-10-05 | 2009-04-09 | Kuraray Europe Gmbh | Photovoltaikmodule mit weichmacherhaltigen Folien auf Basis von Polyvinylacetal mit hohem spezifischen Widerstand |
DE102007055733A1 (de) * | 2007-12-07 | 2009-06-10 | Kuraray Europe Gmbh | Photovoltaikmodule mit reflektierenden Klebefolien |
JP5308444B2 (ja) * | 2007-12-18 | 2013-10-09 | 株式会社クラレ | 合わせガラス用中間膜、その製造方法及びそれを用いた合わせガラス |
WO2010005029A1 (ja) * | 2008-07-11 | 2010-01-14 | 三菱樹脂株式会社 | 太陽電池用バックシート |
EP2153989B1 (de) * | 2008-08-01 | 2021-09-29 | Kuraray Europe GmbH | Mehrschichtfolien aus weichmacherhaltigem Polyvinylacetal mit schalldämpfenden Eigenschaften |
JP5523136B2 (ja) * | 2009-02-18 | 2014-06-18 | 三菱樹脂株式会社 | 合わせガラス用ポリエステルフィルム |
JP5423271B2 (ja) * | 2009-04-16 | 2014-02-19 | セントラル硝子株式会社 | 自動車のフロントガラス用合わせガラスの製造方法 |
-
2012
- 2012-03-29 BR BR112013024559A patent/BR112013024559A2/pt not_active IP Right Cessation
- 2012-03-29 CN CN201510146229.0A patent/CN104816522B/zh not_active Expired - Fee Related
- 2012-03-29 CN CN201280015902.1A patent/CN103476841B/zh not_active Expired - Fee Related
- 2012-03-29 MX MX2013011187A patent/MX2013011187A/es active IP Right Grant
- 2012-03-29 JP JP2012538127A patent/JP5155497B2/ja not_active Expired - Fee Related
- 2012-03-29 KR KR1020137028646A patent/KR101375204B1/ko active IP Right Grant
- 2012-03-29 RU RU2013147980/05A patent/RU2013147980A/ru not_active Application Discontinuation
- 2012-03-29 EP EP12763997.9A patent/EP2692781A4/en not_active Withdrawn
- 2012-03-29 WO PCT/JP2012/058406 patent/WO2012133668A1/ja active Application Filing
- 2012-03-29 US US14/008,745 patent/US9431560B2/en not_active Expired - Fee Related
- 2012-12-06 JP JP2012267633A patent/JP5301724B2/ja not_active Expired - Fee Related
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KR101375204B1 (ko) | 2014-03-17 |
MX2013011187A (es) | 2013-12-16 |
US9431560B2 (en) | 2016-08-30 |
EP2692781A1 (en) | 2014-02-05 |
CN104816522B (zh) | 2017-09-15 |
JP5301724B2 (ja) | 2013-09-25 |
WO2012133668A1 (ja) | 2012-10-04 |
JP5155497B2 (ja) | 2013-03-06 |
MX336684B (es) | 2016-01-27 |
JP2013091793A (ja) | 2013-05-16 |
KR20130130870A (ko) | 2013-12-02 |
RU2013147980A (ru) | 2015-05-10 |
BR112013024559A2 (pt) | 2016-12-20 |
CN103476841B (zh) | 2015-04-29 |
US20140020759A1 (en) | 2014-01-23 |
EP2692781A4 (en) | 2014-09-03 |
CN104816522A (zh) | 2015-08-05 |
CN103476841A (zh) | 2013-12-25 |
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