JP4427324B2 - ポリビニルアルコールをベースとするプラスチックの熱可塑性加工方法 - Google Patents
ポリビニルアルコールをベースとするプラスチックの熱可塑性加工方法 Download PDFInfo
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 65
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 60
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 15
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 15
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- 238000000034 method Methods 0.000 claims abstract description 50
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 53
- 239000004014 plasticizer Substances 0.000 claims description 29
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 150000004072 triols Chemical class 0.000 claims description 3
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- 229920001577 copolymer Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- -1 propylene diglycol Chemical compound 0.000 description 8
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- 238000005259 measurement Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- 238000007872 degassing Methods 0.000 description 4
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- 150000002334 glycols Chemical class 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 238000010137 moulding (plastic) Methods 0.000 description 4
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- 238000007906 compression Methods 0.000 description 3
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- 229920003002 synthetic resin Polymers 0.000 description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RLRFALRYCGSYPP-UHFFFAOYSA-N prop-2-enamide;prop-1-ene-1-sulfonic acid Chemical compound NC(=O)C=C.CC=CS(O)(=O)=O RLRFALRYCGSYPP-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/201—Pre-melted polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Description
a.)15.0〜99.9重量%の、好ましくは25.0〜99.9重量%の、有利には40.0〜99.9重量%の、特に50.0〜99.9重量%の式(1)の構造単位と、
各基R1は、相互に独立に、水素またはメチル、好ましくは水素である。
基R2は1〜6個の炭素原子を有するアルキル基、有利にはメチル、エチル、n−プロピル、i−プロピル、n−ブチル、s−ブチル、t−ブチル、n−ペンチル、またはn−ヘキシル基、極めて有利にはメチルあるいはエチル基、特にメチル基を示す。
それゆえ、本発明は、本発明の方法により得られる成形品も提供する。
それゆえ、本発明は、包装材料としての本発明の成形品の使用も提供する。
Mettlerのロボット支援のDSC820装置を用いてDSC測定を行う。20℃/分の加熱速度を用いて、−10℃〜250℃で測定を行う。材料を各々の場合、20℃/分で加熱および冷却し、合計3個の測定曲線(第1の加熱、第1の冷却、および第2の加熱)を得る。試料から秤取する量は、各々の場合約10mgである。
ポリビニルアルコールペレットの製造
表1〜3に示す配合物を27mmのスクリュー直径、40のL/D、および9つの加熱ゾーンを持つZSE 27 GL 1200 Leistritz2軸スクリュー押し出し機で押し出す。個々の加熱ゾーンの温度設定を表4〜5に示す。真空脱気を37Dで使用する。孔あきダイを使用して、ストランドを製造する。得られるストランドは均質で、ふくれを含まない。使用される冷却方法は、空冷および水浴冷却付きのメッシュベルトであり、下流でペレット化する。
1000kNの型締力、36mmのスクリュー直径、開放ノズル、螺旋型を用いる最大射出容積152mlのRICO射出成形機で実施例1において製造されたペレットを加工して、厚さ2mm、幅8mm、および長さ44cmの寸法の均質な螺旋を得る。
加熱ゾーンの設定:
ゾーン1:160℃
ゾーン2〜4:170℃
この螺旋は、非溶融分を含まないと視覚的に評価される。
強制循環ミキサーを用いて調製される同一配合のブレンド(Kunstharz−Nachrichten,issue 14,pp.1〜6,1978におけるようなブレンド調製物)と比較して、実施例2、3、7、10、11、12、14、および16において製造されるペレットを実施例17に類似して射出成形機で加工して、種々の長さの螺旋を得る。
完全に加水分解されたポリビニルアルコールを含む配合物に対して、および比較的に高粘度の部分的に加水分解された物を含む配合物に対しても、加熱ゾーンの温度プロフィールを10〜40℃だけ上昇させる。
強制循環ミキサーを用いて調製される同一配合のブレンド(Kunstharz−Nachrichten,issue 14,pp.1〜6,1978におけるようなブレンド調製物)と比較して、実施例2において製造されたペレットを一定に増加する谷径のスクリューを用いる30mmの単軸スクリュー、L/D=25、30mmのダイ直径、0.6mmのダイ幅のGoettfertブローフィルム押し出し機で50rpmの回転速度と3.5kg/時の処理量で押し出して、約20μmの厚さのブローフィルムを得る。
スクリュー圧縮比:1:4
加熱ゾーンの設定:
ゾーン1および2:205℃
ゾーン3:200℃
ゾーン4〜6:195℃
ダイ:170℃
強制循環ミキサーを用いて製造される同一配合のブレンド(Kunstharz−Nachrichten,issue 14,pp.1〜6,1978におけるようなブレンド調製物)と比較して、実施例26と同じように実施例4、5、6、8、9、13、および15において製造されたペレットをGoettfertブローフィルム押し出し機で押し出して、ブローフィルムを得て、フィッシュアイを分析した。
ポリビニルアルコールペレットの製造
表6に示す配合物を27mmのスクリュー直径、40のL/D、および9個の加熱ゾーンを有するZSE 27 GL 1200Leistritz2軸スクリュー押し出し機で押し出す。個々の加熱ゾーンに対する温度設定を表7に示す。真空脱気を37Dで使用する。孔あきダイを使用して、ストランドを製造する。得られたストランドは均質で、ふくれを含まない。使用される冷却方法は、空冷および水浴冷却付きのメッシュベルトであり、下流でペレット化する。
フィッシュアイ頻度評価を表8に示す。
ポリビニルアルコールペレットの製造
表9に示す配合物を27mmのスクリュー直径、40のL/D、および9個の加熱ゾーンを有するZSE 27 GL 1200 Leistritz2軸スクリュー押し出し機で押し出す。個々の加熱ゾーンに対する温度設定を表10に示す。真空脱気を37Dで使用する。孔あきダイを使用してストランドを製造する。得られたストランドは均質で、ふくれを含まない。使用される冷却方法は、空冷およびまた水浴冷却付きのメッシュベルトであり、下流でペレット化する。
フィッシュアイ頻度評価を表11に示す。
Claims (7)
- 少なくとも1つのポリマー(A)と、少なくとも1つの可塑剤と、水および/または他の添加物とを熱可塑性加工する方法であって、
ここで、ポリマー(A)は、いずれもポリマー(A)の全重量基準で、
a.)15.0〜99.9重量%の式(1)の構成単位と、
b.)0.0〜50.0重量%の式(2)の構造単位と、
c.)0.0〜50.0重量%の式(3)の構造単位
を含むものであって、
ポリマー(A)と可塑剤を水の含量が、ポリビニルアルコール基準で2重量%未満で予備混合せずに押し出し機の中に導入すること及び押し出し機のシリンダーとダイが加熱されていることを特徴とする方法。 - 押し出し機が次のシリンダー温度を有することを特徴とする請求項1に記載の方法、
取り入れ区域:20〜60℃の範囲
溶融および均質化区域:130〜250℃の範囲
排出区域:170〜230℃の範囲。 - 70〜100モル%の範囲の加水分解度と、4重量%水溶液で測定して2〜70mPasの範囲の粘度のポリビニルアルコールを使用することを特徴とする請求項1または2に記載の方法。
- 使用される可塑剤が多価アルコール、及びそれらの誘導体、ポリエチレングリコール、グリセロール、ジオール、およびトリオール、ならびにそれらの混合物を含むことを特徴とする請求項1〜3のいずれかに記載の方法。
- 使用される他の添加物が潤滑剤、固結防止剤、酸化防止剤、顔料、染料、固体可塑剤、充填剤、および/または他のポリマー化合物を含むことを特徴とする請求項1〜4のいずれか1つに記載の方法。
- 熱可塑性加工が溶融押し出しにより行われることを特徴とする請求項1〜5のいずれか1つに記載の方法。
- ポリマー(A)が内部可塑化されたものであることを特徴とする請求項1〜6のいずれか1つに記載の方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10142922A DE10142922A1 (de) | 2001-09-01 | 2001-09-01 | Polyvinylalkohol-Formkörper, Verfahren zu deren Herstellung mittels thermoplastischer Verfahren sowie deren Verwendung |
PCT/EP2002/009664 WO2003020823A1 (de) | 2001-09-01 | 2002-08-30 | Kunststoff-formkörper auf basis von polyvinylalkohol, verfahren zu deren herstellung mittels thermoplastischer verfahren sowie deren verwendung |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005501763A JP2005501763A (ja) | 2005-01-20 |
JP4427324B2 true JP4427324B2 (ja) | 2010-03-03 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2003525087A Expired - Fee Related JP4427324B2 (ja) | 2001-09-01 | 2002-08-30 | ポリビニルアルコールをベースとするプラスチックの熱可塑性加工方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US20050001348A1 (ja) |
EP (1) | EP1421140B1 (ja) |
JP (1) | JP4427324B2 (ja) |
AT (1) | ATE314423T1 (ja) |
CA (1) | CA2453952C (ja) |
DE (2) | DE10142922A1 (ja) |
DK (1) | DK1421140T3 (ja) |
ES (1) | ES2252514T3 (ja) |
WO (1) | WO2003020823A1 (ja) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10241466B4 (de) * | 2001-12-14 | 2006-05-24 | Henkel Kgaa | Inline Blenden und Formgeben wasserlöslicher Polymere |
DE202004012387U1 (de) * | 2003-08-19 | 2004-10-28 | Kuraray Specialities Europe Gmbh | Polyvinylacetal-haltiges Granulat |
GB2409204A (en) | 2003-12-19 | 2005-06-22 | Reckitt Benckiser Nv | Plasticized thermoplastic polymer |
US20050163948A1 (en) | 2004-01-28 | 2005-07-28 | Mcgarel Owen J. | Smokable polymeric casing |
US20060214050A1 (en) * | 2004-11-17 | 2006-09-28 | Naeckel Arno T | Disposable variable depth anchor cable pack |
US20080059395A1 (en) | 2006-01-10 | 2008-03-06 | Manyworlds, Inc. | Adaptive Online Experimentation |
US7781506B2 (en) * | 2007-01-26 | 2010-08-24 | E.I. Du Pont De Nemours And Company | Poly(vinyl alcohol) composition comprising a polyol |
WO2008093615A1 (ja) | 2007-01-31 | 2008-08-07 | The Nippon Synthetic Chemical Industry Co., Ltd. | ポリビニルアルコール系樹脂組成物およびフィルム |
JP5464863B2 (ja) * | 2009-01-19 | 2014-04-09 | 旭有機材工業株式会社 | 発泡性レゾール型フェノール樹脂成形材料およびその製造方法ならびにフェノール樹脂発泡体 |
HUE044223T2 (hu) * | 2010-01-29 | 2019-10-28 | Monosol Llc | PVOH polimerek keverékét tartalmazó javított vízoldható film és az abból elõállított csomagolás |
WO2012013945A1 (en) * | 2010-07-30 | 2012-02-02 | Neil Goodenough | Ophthalmic device molds and related methods |
ES2865503T3 (es) * | 2015-01-22 | 2021-10-15 | Hollister Inc | Catéteres urinarios lubricados que tienen flexibilidad variable |
US10316120B2 (en) | 2015-09-18 | 2019-06-11 | Aquapak Polymer Limited | Process and apparatus for manufacture of processable polyvinyl alcohol |
PL3529057T3 (pl) | 2016-10-18 | 2020-09-21 | Kuraray Co., Ltd. | Zastosowanie poli(alkoholu winylowego) o niskiej zawartości octanu sodu w procesie drukowania 3D |
JP6934947B2 (ja) | 2016-10-18 | 2021-09-15 | 株式会社クラレ | ポリビニルアルコールと低極性ポリマーとの混合物の3d印刷法における支持構造体としての使用 |
DE102017004563A1 (de) | 2017-03-05 | 2018-09-06 | Entex Rust & Mitschke Gmbh | Entgasen beim Extrudieren von Polymeren |
DE102018001412A1 (de) | 2017-12-11 | 2019-06-13 | Entex Rust & Mitschke Gmbh | Entgasen beim Extrudieren von Stoffen, vorzugsweise von Kunststoffen |
WO2020047139A1 (en) | 2018-08-28 | 2020-03-05 | Kuraray Co., Ltd. | Diverting agents based on thermoplastic polyvinyl alcohol pellets |
CN111087725B (zh) * | 2018-10-23 | 2023-07-04 | 中国石油化工股份有限公司 | 低粘度聚乙烯醇组合物及其制备方法和应用 |
EP3878285A1 (en) | 2020-03-12 | 2021-09-15 | Kuraray Co., Ltd. | Synthetic food casings comprising polyvinyl alcohols and method for their fabrication |
EP3936555A1 (en) * | 2020-07-06 | 2022-01-12 | Aquapak Polymers Limited | Plasticised polyvinyl alcohol mixture and method for making it. |
WO2023180323A1 (en) | 2022-03-22 | 2023-09-28 | Viscofan España, S.L.U. | Thermoplastic film and packaging made of such thermoplastic film useful to sterilize objects |
EP4321660A1 (en) * | 2022-08-13 | 2024-02-14 | Aquapak IP Limited | Polyvinyl alcohol fibres and fibrous products |
EP4332151A1 (en) | 2022-08-31 | 2024-03-06 | Aquapak IP Limited | Cellulose fibre reinforced polyvinyl alcohol composite materials |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3991153A (en) * | 1975-06-24 | 1976-11-09 | American Cyanamid Company | Single phase extrusion of acrylic polymer and water |
DE2964688D1 (en) * | 1978-03-23 | 1983-03-17 | Hoechst Ag | Polyvinyl alcohol pellets containing a plasticizer, and method for their preparation |
US4618648A (en) * | 1985-04-26 | 1986-10-21 | Air Products And Chemicals, Inc. | Copolymers of vinyl alcohol and poly(alkyleneoxy)acrylates |
US4611019A (en) * | 1985-06-17 | 1986-09-09 | Lutzmann H Harald | Enhanced barrier compositions from polyvinyl alcohol |
NZ234921A (en) * | 1989-09-01 | 1993-02-25 | Air Prod & Chem | Polyvinyl alcohol pellet prepared by melt extrusion |
US5028648A (en) * | 1990-07-12 | 1991-07-02 | Air Products And Chemicals, Inc. | Extrudable polyvinyl alcohol compositions containing thermoplastic polyurethane |
EP0635545A3 (en) * | 1993-07-21 | 1995-07-12 | Air Prod & Chem | Injection molded articles made from extrudable polyvinyl alcohol compositions. |
JP4472100B2 (ja) * | 2000-04-03 | 2010-06-02 | 株式会社クラレ | ポリビニルアルコール系樹脂組成物 |
-
2001
- 2001-09-01 DE DE10142922A patent/DE10142922A1/de not_active Withdrawn
-
2002
- 2002-08-30 ES ES02772231T patent/ES2252514T3/es not_active Expired - Lifetime
- 2002-08-30 CA CA2453952A patent/CA2453952C/en not_active Expired - Lifetime
- 2002-08-30 JP JP2003525087A patent/JP4427324B2/ja not_active Expired - Fee Related
- 2002-08-30 DE DE50205458T patent/DE50205458D1/de not_active Expired - Lifetime
- 2002-08-30 EP EP02772231A patent/EP1421140B1/de not_active Expired - Lifetime
- 2002-08-30 WO PCT/EP2002/009664 patent/WO2003020823A1/de active IP Right Grant
- 2002-08-30 US US10/487,702 patent/US20050001348A1/en not_active Abandoned
- 2002-08-30 DK DK02772231T patent/DK1421140T3/da active
- 2002-08-30 AT AT02772231T patent/ATE314423T1/de active
Also Published As
Publication number | Publication date |
---|---|
CA2453952C (en) | 2011-03-22 |
WO2003020823A1 (de) | 2003-03-13 |
EP1421140A1 (de) | 2004-05-26 |
ES2252514T3 (es) | 2006-05-16 |
CA2453952A1 (en) | 2003-03-13 |
JP2005501763A (ja) | 2005-01-20 |
EP1421140B1 (de) | 2005-12-28 |
US20050001348A1 (en) | 2005-01-06 |
DE10142922A1 (de) | 2003-03-20 |
DK1421140T3 (da) | 2006-04-18 |
DE50205458D1 (de) | 2006-02-02 |
ATE314423T1 (de) | 2006-01-15 |
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