JP5192750B2 - 硬化性組成物 - Google Patents
硬化性組成物 Download PDFInfo
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- JP5192750B2 JP5192750B2 JP2007209445A JP2007209445A JP5192750B2 JP 5192750 B2 JP5192750 B2 JP 5192750B2 JP 2007209445 A JP2007209445 A JP 2007209445A JP 2007209445 A JP2007209445 A JP 2007209445A JP 5192750 B2 JP5192750 B2 JP 5192750B2
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- binder
- starch
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- 239000011087 paperboard Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000003976 plant breeding Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940071440 soy protein isolate Drugs 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
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- 229940014800 succinic anhydride Drugs 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
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- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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- 238000004078 waterproofing Methods 0.000 description 1
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- 229940100445 wheat starch Drugs 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C08K5/16—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/22—Proteins
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paper (AREA)
Description
(a)5〜40重量%のカルボキシ酸モノマーをコポリマー中に有する少なくとも1種のポリカルボキシエマルジョンコポリマー;
(b)少なくとも2個のヒドロキシ基を有する少なくとも1種のヒドロキシアミド架橋剤;
多糖または植物性タンパク質、またはその混合物からなる群から選択される少なくとも1種のエキステンダーであって、全組成物バインダー固形分基準の重量パーセントで5〜70%で存在するエキステンダー:を含むバインダー組成物である。本発明の他の態様を以下で論議する。
繊維の湿潤未硬化ウェブを形成し、好ましくはバインダー適用ステーションを通って移動する移動式スクリーンに移し、ここで本発明の水性バインダーがマットに適用される方法を包含する。バインダーは、例えば、エアまたはエアレススプレー、パッディング、含浸、ロールコーティング、カーテンコーティング、ビーター堆積、凝固またはディップおよびスクイーズ適用などの任意の適当な手段により構造物に適用することができ、支持ワイヤまたはスクリーン上に置かれた、得られた飽和湿潤バインダーウェブを1以上の真空ボックス上に流して、マット中の所望のバインダー含量を達成するために十分なバインダーを除去する。本発明のマット中のバインダー量は、完成乾燥マットの約10〜約35重量パーセント、好ましくは約15〜約30重量パーセント、最も好ましくは約20〜約30重量パーセント、例えば、約25±3重量パーセントの範囲でありうる。バインダー組成物は熱を加えることにより硬化することができる。すなわち、バインダー組成物は熱硬化性組成物である。
エマルジョンポリマー合成例1〜7
すべてのラテックスサンプルを同じ手順により調製した。パドルスターラー、熱電対、窒素インレット、および還流コンデンサーを備えた3リットルの丸底フラスコに、780グラムの脱イオン水を入れ、88℃に加熱し、この温度で13.0グラムの脱イオン水中に溶解させた1.95グラムの過硫酸アンモニウムの溶液を脱イオン水とともにこの温度で添加する。2分後、91.7グラムの100nmラテックスシード(固形分45%)を入れ、続いて2分間保持する。表Aに示したレシピに従ってモノマーエマルジョンを調製した。2分後、反応温度を88℃に維持しながら、モノマーエマルジョンおよび1.95グラムの過硫酸アンモニウムの102グラムの脱イオン水中の別の溶液をゆっくりと3時間かけて添加した。この添加が完了した後、反応混合物を88℃で20分間保持し、次いで70℃に冷却した。7.8ミリグラムの硫酸鉄七水和物の5.2グラムの脱イオン水中溶液を反応混合物に添加した。18.0グラムの脱イオン水で希釈された3.64グラムの水性tert−ブチルヒドロパーオキシド(70%)の溶液および1.82グラムのイソアスコルビン酸の19.5グラムの脱イオン水中の溶液をゆっくりと15分にわたって反応混合物に添加した。反応混合物を70℃でさらに15分間保持し、次いで冷却した。得られたラテックスはほぼ39.5%の固形分を有していた。
β−ヒドロキシアミド#1 ε−カプロラクトンおよびジエタノールアミンの反応生成物
コンデンサー、熱電対、およびメカニカルスターラーを備えた1Lのフラスコに、157.5グラム(1.5モル)のジエタノールアミン(DEOA)を添加した。室温、1気圧の窒素下で、外部加熱なしに始めて、171.2グラム(1.5モル)のε−カプロラクトンを反応フラスコにピペットで少量ずつ1時間かけて添加した。反応混合物は若干の発熱を示して31℃になった。ε−カプロラクトンの添加が完了した後、反応混合物をさらに1時間撹拌した。その後、82.0グラムの脱イオン水を添加して、80%の活性物質を得た。
ベータ−ヒドロキシアミド#2 γ−ブチロラクトンおよびジエタノールアミンの反応生成物
コンデンサー、熱電対、およびメカニカルスターラーを備えた1Lのフラスコに、157.5グラム(1.5モル)のDEOAを添加した。室温、1気圧の窒素下で、外部加熱なしに始めて、127.9グラム(1.5モル)のγ−ブチロラクトンを反応フラスコにピペットで少量ずつ1.5時間かけて添加した。反応混合物は若干の発熱を示して27℃になった。γ−ブチロラクトンの添加が完了した後、反応混合物をさらに1時間撹拌した。その後、69.8グラムの脱イオン水を添加して、80%の活性物質を得た。
デンプン調製
以下のバインダーサンプル1〜13について、デンプンを次のように処理する。1クオートのステンレス鋼製容器に、490グラムの水を量り取り、予熱され、85℃に維持された水浴中に容器をクランプで固定した。水浴中の水面を、容器中の水面よりも高く維持した。ベンチトップスターラーに取り付けた撹拌ブレードを、容器の側面または底面に当たらないように水中に配置した。スターラーを強力な渦が生じるために十分な速度で作動させる。210グラムのデンプン(Penford Gum290)を紙コップ中に量り取り、次いで撹拌された水にゆっくりと添加した。この温度で、時間の測定が開始され、混合物を25分間85℃で加熱処理する。25分間の加熱処理時間の後、混合物を水浴から取り出す。バインダー配合物に添加する前に、デンプン混合物を室温の水で約10〜15%固形分に希釈し、一定濃度になるように撹拌する。
比較例Aは、重量比90/10のアクリルエマルジョンと尿素ホルムアルデヒド樹脂のブレンドである。比較例Bはバインダーであって;トリエタノールアミンで架橋された、100%アクリル酸の可溶性ポリマーからなる。
水吸収試験結果
デンプン/多塩基性酸(クエン酸)調製
以下のバインダーサンプル14〜15について、より低い分子量のデンプンを使用する以外は前記実施例10と同様にデンプンを加工し、クエン酸とともに加熱処理して、デンプンヒドロキシル官能基についての反応性部位を得る。1クオートのステンレス鋼製容器に、558.86グラムの水を量り取り、予熱され、85℃に維持された水浴中に容器をクランプで固定する。水浴中の水面を容器中の水面よりも高く維持する。ベンチトップスターラーに取り付けられた撹拌ブレードを、容器の側面または底部に当たらないように水中に配置する。スターラーを強力な渦が生じるために十分な速度で作動させる。270グラムのデンプン(Penford Gum 295)を紙コップ中に量り取り;30グラムの無水クエン酸を、デンプンを含む同じコップ中に量りとる。次いで、この乾燥混合物を、加熱された水浴中に固定された撹拌水に添加する。この温度で、時間の測定が開始され、混合物を25分間85℃で加熱処理する。25分間の加熱処理時間の後、混合物を水浴から取り出す。バインダー配合物に添加する前に、デンプン/クエン酸混合物を室温の水で約10〜15%固形分に希釈し、一定の濃度になるように撹拌する。
熱時および室温引っ張り試験結果:サンプル14〜16
マット調製:
市販のポリエステルスパンボンドマット(未処理)を15”×12”(38.10cm×30.48cm)シートに切り出す。シートを11%浴固形分(重量)の試験バインダー配合物中でディップコーティングする。浸漬されたシートを40psiでパディングし、直後に200℃で3分間硬化させる。バインダー追加物は約20重量%である。
硬化シートを2”×12”(5.08cm×30.48cm)試験片に切り出す。引っ張り試験機のオーブンチャンバーを試験前に375°F(190℃)に予熱する。予熱されたら試験片をジョー中に置き、オーブンチャンバーを閉じ、375°F(190℃)で平衡化させる。サンプルを次いで、8インチ(20.32cm)/分のクロスヘッド速度、8”(20.32cm)ギャップで引き離す。熱時引っ張り強度を20%伸長(ひずみ)で測定し、ニュートンで表す。試験片の幅を狭い点で測定し、これを初期幅で割ることにより、熱時幅保持性を計算し、パーセントとして表す。熱時幅保持性は基体の熱寸法安定性の尺度である。
水溶性色素の水中混合物を1クォートガラスジャーに底部から20mmの高さまで添加する。硬化シートの2”×10”(15.08cm×25.40cm)試験片をジャー中で縦方向に配置する。すべての硬化シートサンプルをガラスジャー中で同じ角度で配置する。水が硬化シートを上昇する垂直高さを、水溶性色素溶液中での48時間の浸漬後に記録する。
Claims (10)
- (a)0〜70℃のガラス転移温度(Tg)を有し、5〜45重量%のカルボキシ酸モノマーを共重合単位として有する少なくとも1種のポリカルボキシエマルジョンコポリマー;
(b)少なくとも2個のヒドロキシ基を有する少なくとも1種のβ−ヒドロキシアルキルアミド架橋剤;
多糖もしくは植物性タンパク質、またはその混合物(多糖、植物性タンパク質、およびその混合物はそれぞれ水性溶媒に可溶である)からなる群から選択される少なくとも1種のエキステンダーであって、全組成物バインダー固形分基準の重量パーセントで5〜80%で存在するエキステンダー:
を含み、デンプンがエキステンダーとして用いられる場合、デンプンは基体に適用される前に加熱処理され、デンプンが基体に適用される前または後のいずれかに、他のバインダー成分が加熱処理されたデンプンと混合される、バインダー組成物。 - カルボキシ酸モノマーがアクリル酸である請求項1記載のバインダー組成物。
- アクリル酸がポリカルボキシエマルジョンコポリマーの10〜20重量%である請求項2記載のバインダー組成物。
- ポリカルボキシエマルジョンポリマーが0〜35℃の測定されたTgを有する請求項3記載のバインダー組成物。
- ポリカルボキシエマルジョンポリマーが35〜70℃の測定されたTgを有する請求項3記載のバインダー組成物。
- エキステンダーが10000未満の重量平均分子量を有する水溶性デンプンを含む請求項1記載のバインダー組成物。
- エキステンダーが10000から10000000の間の重量平均分子量を有する水不溶性デンプンを含む請求項1記載のバインダー組成物。
- 少なくとも2個のカルボン酸基、無水物基、またはその塩を含有する可溶性付加ポリマーまたはコポリマーをさらに含む請求項1記載のバインダー組成物。
- エマルジョンコポリマーがアクリロニトリルを含む請求項1記載のバインダー組成物。
- エキステンダーがクエン酸と共に加熱処理済みである請求項1記載のバインダー組成物。
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-
2007
- 2007-06-19 US US11/820,357 patent/US7829611B2/en not_active Expired - Fee Related
- 2007-08-10 JP JP2007209445A patent/JP5192750B2/ja not_active Expired - Fee Related
- 2007-08-15 CN CN2007101423412A patent/CN101130677B/zh not_active Expired - Fee Related
- 2007-08-15 ES ES07253197T patent/ES2372623T3/es active Active
- 2007-08-15 EP EP07253197A patent/EP1892273B1/en not_active Expired - Fee Related
- 2007-08-23 KR KR1020070084758A patent/KR100850251B1/ko not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
CN101130677B (zh) | 2010-12-01 |
KR100850251B1 (ko) | 2008-08-04 |
CN101130677A (zh) | 2008-02-27 |
EP1892273A2 (en) | 2008-02-27 |
JP2008075071A (ja) | 2008-04-03 |
EP1892273A3 (en) | 2008-10-15 |
ES2372623T3 (es) | 2012-01-24 |
US20080051539A1 (en) | 2008-02-28 |
KR20080018820A (ko) | 2008-02-28 |
US7829611B2 (en) | 2010-11-09 |
EP1892273B1 (en) | 2011-10-19 |
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