TWI810236B - 製造具有改良的填料保留性及不透明性同時維持濕拉伸強度之紙類的方法 - Google Patents
製造具有改良的填料保留性及不透明性同時維持濕拉伸強度之紙類的方法 Download PDFInfo
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- TWI810236B TWI810236B TW108101584A TW108101584A TWI810236B TW I810236 B TWI810236 B TW I810236B TW 108101584 A TW108101584 A TW 108101584A TW 108101584 A TW108101584 A TW 108101584A TW I810236 B TWI810236 B TW I810236B
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Classifications
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- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
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- D21H17/20—Macromolecular organic compounds
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- 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
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- D—TEXTILES; PAPER
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- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- 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
- D21H17/33—Synthetic macromolecular compounds
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- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
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- 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
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- 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
- D21H17/33—Synthetic macromolecular compounds
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- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
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- 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
- D21H17/33—Synthetic macromolecular compounds
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- D—TEXTILES; PAPER
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- 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
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- D21H17/33—Synthetic macromolecular compounds
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- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
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- 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
- D21H17/33—Synthetic macromolecular compounds
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- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
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- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- 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
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- 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
- D21H21/20—Wet strength agents
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- 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
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- D21H21/28—Colorants ; Pigments or opacifying agents
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- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
- D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
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Abstract
本發明揭示一種製造具有改良的填料保留性及不透明性之紙類的方法。該方法包括以下步驟:將添加劑A及添加劑B添加至造紙機之濕端中的漿料中,其中該漿料包含紙漿及填料。添加劑A為濕強度劑。添加劑B為陰離子聚合物,在pH約為6之緩衝液中量測時,以乾重計,該陰離子聚合物具有約-3000至約-7000 ueq/g之電荷密度。添加劑B亦具有約150,000至約1,000,000道爾頓之重量平均分子量。
Description
本發明大體上係關於一種為紙類提供填料保留性及不透明性同時維持濕拉伸強度之方法。更特定言之,本發明係關於添加至造紙機之濕端中之漿料中的濕強度劑及特定陰離子聚合物之用途。
先前技術揭示了改良裝飾(層壓)紙類等級之不同態樣的各種嘗試,參見例如CN102174761、美國專利5679219、JP2011219874、CN102174768、CN102174769、CN101435169、DE102008046856、CN102174761、US2016059530及SU1481307。某些先前技術揭示逐漸增大填料含量,諸如美國專利8163134、美國專利5759346,而其他技術聚焦於不透明性,例如DE102013100353。再其他技術揭示保留性及濾水性,諸如美國專利20040221977。然而,該行業仍需要維持或改良高度填充紙類之填料保留性、不透明性及濕強度。
本發明提供一種製造具有不透明性及填料保留性之紙類之方法。該方法包括以下步驟:將添加劑A及添加劑B添加至造紙機之濕端中的漿料中,其中該漿料包含紙漿及填料。添加劑A為濕強度劑。添加劑B為陰離子聚合物,在pH約為6之緩衝液中量測時,以乾重計,該陰離子聚合物具有約-3000至約-7000 ueq/g之電荷密度。添加劑B亦具有約150,000至約1,000,000道爾頓之重量平均分子量。
本申請案主張2018年1月16日申請之美國臨時申請案第62/617,938號之權益,該申請案明確地以全文引用之方式併入本文中。
本發明中所解決的一個問題為製備紙類,諸如原紙(base paper)。此紙類可用於層壓應用,其展現相對於填料保留性、不透明性及/或濕強度中之至少一者改良的或理想的特性。
在一個實施例中,本發明藉由添加具有特定電荷及/或分子量特性之陰離子共添加劑而改良與基礎PAE樹脂單獨添加相關的此等特性中之一或多者。以此方式,可在對濕拉伸強度無負面影響的情況下製造具有較高水準不透明性及填料保留性之基礎紙張。可替代地,可在未負面地影響紙張之填料保留性及不透明性的情況下持續改良濕拉伸強度。
在其他實施例中,本發明描述一種製造具有較高不透明性及填料保留性同時維持濕拉伸強度之紙類(例如填充紙類等級,尤其裝飾紙類等級)之方法。可替代地,本發明描述一種用於製造具有改良的不透明性及填料保留性同時維持濕拉伸強度之紙類(例如填充紙類等級,尤其裝飾紙類等級)之方法。
在各種實施例中,如藉由Technidyne Brightimeter TAPPI方法T425所量測,紙類在將層壓視為較高不透明性後為至少約80%、85%、90%或95%不透光。在其他實施例中,該方法係關於製造最小基本重量為約50公克/平方公尺(grams per square meter;gsm),典型地至少約55或約60 gsm之紙類。在其他實施例中,該方法包括以下步驟:將兩種添加劑(添加劑A及添加劑B)添加至造紙方法之濕端,例如添加至包括紙漿及填料之漿料中。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
漿料可為造紙技術中已知之任一者且可描述為紙漿漿料或紙漿及填料漿料。漿料可為此項技術中已知之任一者,例如基於原生紙漿、脫墨紙漿(deinked pulp;DIP)、未經漂白牛皮紙漿(unbleached Kraft pulp;UBK)、機械紙漿,如熱機械紙漿(thermal mechanical pulp;TMP)、半化學機械紙漿,如中性亞硫酸鹽半化學品(neutral sulfite semi-chemical;NSSC)、舊瓦楞箱(old corrugated containers;OCC)、回收報紙、回收組織或其他纖維來源。紙漿可以此項技術中已知的任何量存在於漿液中。
在各種實施例中,添加劑A可為或包括濕強度添加劑,諸如聚醯胺基胺環氧氯丙烷(PAE)。添加劑B可為或包括具有下文描述之特定特性的陰離子聚合物。除用於本發明中之此等兩種添加劑及填料之外,其他添加劑可用於造紙方法中。可替代地,漿料可不含或包括小於5重量%、4重量%、3重量%、2重量%、1重量%、0.5重量%或0.1重量%之非添加劑A或B或填料之一或多種添加劑。此等排除添加劑可為下文描述之一或多種視情況存在之添加劑及/或造紙技術中已知之一或多種添加劑。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
在各種實施例中,在pH約為6下量測時,添加劑B為具有在約-3000與約-7000 ueq/g (以乾重計)之間的電荷密度之陰離子聚合物,且具有約150,000至約1,000,000道爾頓之重量平均分子量。在各種實施例中,相較於未利用化學添加劑之比較性方法及/或相較於單獨利用添加劑A之比較性方法,此方法提供改良的不透明性、填料保留性及/或濕拉伸強度。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
用於製造裝飾(層壓)紙類等級之方法典型地涉及使用較高填料負載以為最終層壓產物提供不透明性。層壓方法典型地涉及在水性樹脂中潤濕原紙接著固化。原紙必須具有足夠濕強度以經受後續加工。添加至造紙機器之濕端中之化學添加劑典型地影響填料保留性且因此影響不透明性。在各種實施例中,本發明提供兩種添加劑之用途:具有特定分子量及電荷密度之添加劑B (陰離子聚合物)及添加劑A (濕強度樹脂),典型地為聚醯胺基胺環氧氯丙烷(PAE)。在其他實施例中,本發明提供比藉由PAE單獨製造之紙張之填料保留性及不透明性更佳的填料保留性及不透明性同時維持與藉由PAE單獨製造之紙張之濕拉伸強度類似的濕拉伸強度。由於某些陰離子添加劑將負面地影響該等特性中之一或多者,因此添加劑B之特性在提供全部三種特性時可為至關重要的。儘管本發明係關於裝飾紙類等級,但其亦可應用於任何其他類型之紙類,包括但不限於具有較高填料負載之印刷紙及書寫紙等級。
為解決層壓(裝飾)紙類等級中之較高水準之PAE樹脂之負面影響,將陰離子聚合物結合濕強度劑典型地添加至造紙系統之濕端中。如本文中所使用,術語「層壓(laminating/laminate/laminated)」、「裝飾基礎」或「裝飾」紙類係指藉由較高水準之填料負載製造以便為最終層壓產物提供不透明性之特定紙類等級。高度填充紙類為如根據TAPPI T413 OM-11所量測具有大於約15%灰分含量量測值之紙類。所得高度填充紙類典型地裝載有樹脂顆粒(浸漬前)或經歷樹脂浸漬步驟以使一張紙填充有可固化水性樹脂,諸如三聚氰胺甲醛或酚性甲醛。大體而言,術語「裝飾或裝飾性層壓物」之使用係指具有修飾特性之紙張經浸漬且在熱量及壓力下藉由芯紙層或刨花板(particleboard)合併。在一個實施例中,來自ISO 472之正式定義將裝飾性層壓物指定為包括薄片材料(例如紙、膜、箔或織品)之黏結層之層壓物,其中外層或一側或兩側上之層具有裝飾性平面或多樣化顏色或設計。裝飾性層壓物之類別可進一步分類為若干種類別,包括高壓層壓物、裝飾性連續層壓物、直面板(direct-faces boards)及複合板。用於本發明之上下文中之術語裝飾性層壓物典型地包括製備用於裝飾性紙類層壓方法之基礎紙張。
裝飾性層壓原紙類典型地具有某些機械特性以在經由樹脂浸漬處理後保持完整。樹脂浸漬處理典型地包括將紙張展開且經由定量方法將受控量之樹脂添加至紙張。在大多數情況下,溶劑係經由乾燥而經清除以產生可隨後用於層壓方法中之半固化紙張。隨後將紙張切割成目標大小,組裝或層化且添加至壓機中,其中溫度及壓力用於固化樹脂。在大部分裝飾性層壓物中,三聚氰胺甲醛由於其硬度、清晰度、對化學品之耐受性、染色、濕氣及熱量以及其光穩定性而經使用。歸因於樹脂浸漬及固化步驟之本質,濕強度添加劑典型地用於造紙方法中以將濕強度賦予紙張以允許處理。此允許紙張在經由樹脂浸漬步驟及(若可行)堆疊及固化後保持完整。已使用各種濕強度化學物質,但最常見聚醯胺基胺環氧氯丙烷(PAE)樹脂係用於造紙方法之濕端。在各種非限制性實施例中,PAE樹脂之結構描述於美國專利9719212及US 6429267中,該等專利中之各者以引用之方式併入本文中。用於本發明之PAE為水溶性聚合物且用於為紙類提供濕強度。若干種PAE樹脂為可商購的且以各種名稱出售,包括KymeneTM
(Solenis LLC, Wilmington, DE)、FennostrengthTM
(Kemira, Helsinki, 芬蘭)及MaresinTM
(Mare SpA, Milan, 意大利)。
基礎紙張典型地具有足以為最終層壓物提供所需不透明性之不透明性。在浸漬及固化前之紙張中,不透明性係歸因於纖維素纖維及填料顆粒兩者。在樹脂浸漬及固化後,纖維素纖維之折射率改變為近似空氣之折射率。因此,紙張不透明性為填料負載及分佈之功能。典型填料負載可為至多約60重量%之紙張。填料典型地為二氧化鈦。然而,填料可替代地為或包括黏土、碳酸鈣及/或熟習此項技術者已知之其他填料(包括顏料及染料)。二氧化鈦歸因於其光學及光散射特性而為典型填料,但的確具有較高成本。二氧化鈦可屬於銳鈦礦(anatase)或金紅石(rutile)類型。許多製造商之目標為將儘可能多的填料保留在紙中,但此係以獲得用於填料負載之最佳不透明性之方式進行。填料顆粒應均勻地分散在整個紙張中且避免過度絮凝。
如本文中所使用,術語「保留性」或「填料保留性」係指紙張中之填料保留性,而非碎屑及纖維之填料保留性。此係以保留在最終紙張中之投與填料顆粒之量計的量測值,如藉由使用此項技術中已知之任何方法之灰分分析所測定。
在各種實施例中,本發明揭示:具有特定分子量及電荷密度特性之陰離子添加劑(添加劑B)結合添加劑A之用途提供(改良的)填料保留性、不透明性及濕強度三個特性,該等特性對於層壓紙類等級至關重要。標準高分子量填料保留性助劑能夠提供優於藉由PAE樹脂單獨之基礎情況的改良的填料保留性及不透明性,但濕強度受到負面影響。濕強度樹脂及本發明中描述之陰離子添加劑B之組合能夠提供大於標準填料保留性助劑之填料保留性及不透明性改良,同時亦提高紙張之濕拉伸尖峰負載及濕拉伸指數。因此,全部三種特性係經由此陰離子添加劑B及添加劑A之組合改良。
添加劑A為濕強度劑,典型地聚醯胺基胺環氧氯丙烷(PAE)樹脂,且添加劑B為陰離子聚合物或共添加劑。在存在紙漿光纖及填料顆粒的情況下,濕端中之添加物A及添加物B之組合允許相對於藉由單獨給與添加物A之改良的填料保留性、不透明性及濕拉伸強度。出乎意料地,已發現即使在相同經添加化學電荷密度下,使用添加劑B提供高於添加劑A單獨之填料保留性及不透明性水準的填料保留性及不透明性水準。因此,添加劑B之作用係歸因於協同效應,而非僅陽離子樹脂分子之電荷平衡。相較於添加劑A單獨之情況,用於本發明中之陰離子添加劑B提供改良的填料保留性及不透明性以及濕拉伸特性。
添加劑A典型地包括濕強度劑。添加劑A可為以下中之任意一或多者:三聚氰胺甲醛、脲甲醛、乙醛酸化聚丙烯醯胺、聚醯胺基胺環氧氯丙烷及熟習此項技術已知之其他者。典型添加劑A包括聚醯胺基胺環氧氯丙烷濕強度樹脂。
添加劑B典型地包括陰離子聚合物,包括但不限於丙烯酸類聚合物、丙烯醯胺及丙烯酸或甲基丙烯酸之共聚物、羧甲基纖維素(CMC)、陰離子修飾之聚乙烯醇及熟習此項技術者已知之其他陰離子聚合物。
在各種實施例中,添加劑B包括陰離子聚合物,包括但不限於陰離子聚丙烯醯胺共聚物、陰離子聚丙烯醯胺三聚物、羧甲基纖維素、瓜爾豆膠(guar gum)衍生物、經修飾陰離子聚乙烯醇及其組合及熟習此項技術者已知之其他陰離子聚合物。
當添加劑B為聚丙烯醯胺時,其可基於丙烯醯胺、甲基丙烯醯胺、乙基丙烯醯胺及其類似物中之一或多者結合一或多種陰離子單體,諸如丙烯酸甲基丙烯酸丙烯酸酯丙烯酸鹽(包括鈉鹽、鉀鹽及銨鹽及其類似物)、伊康酸、反丁烯二酸、丁烯酸、甲基順丁烯二酸、順丁烯二酸及其鹽、2-丙烯醯胺基-2-甲基丙烷磺酸、2-醯基醯胺基-2-甲基丙烷磺酸、苯乙烯磺酸、乙烯基磺酸及其類似物中之一或多者。用於形成聚丙烯醯胺之額外單體可包括N-乙烯吡咯啶酮、N,N-二烯丙基甲基丙烯醯胺、甲基丙烯酸羥基烷酯、N-乙烯基甲醯胺及其類似物。少量其他可共聚單體,諸如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯腈、乙酸乙烯酯、苯乙烯及其類似物亦可用於進一步修飾聚丙烯醯胺。
添加劑B可為基於聚乙烯醇之陰離子聚合物或陰離子官能化聚乙烯醇。添加劑B可進一步包括一或多種陰離子單體,諸如丙烯酸、甲基丙烯酸、丙烯酸酯、丙烯酸鹽(包括鈉鹽、鉀鹽及銨鹽)、伊康酸、反丁烯二酸、丁烯酸、甲基順丁烯二酸、順丁烯二酸及其鹽、2-丙烯醯胺基-2-甲基丙烷磺酸、2-醯基醯胺基-2-甲基丙烷磺酸、苯乙烯磺酸、乙烯基磺酸、N-乙烯吡咯啶酮、N,N-二烯丙基甲基丙烯醯胺、甲基丙烯酸羥基烷酯、N-乙烯基甲醯胺及其組合中之一或多者。
當藉由Mütek顆粒電荷偵測器或其他基於滴定之串流電流偵測器量測時,添加劑B具有特定電荷密度。當在pH約為6之緩衝液中量測時,電荷密度典型地為約-3000至約-7000 ueq/g乾聚合物,更典型地為約-4000至約-6000 ueq/g,且最典型地為約-5000至約-5500 ueq/g。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
在各種實施例中,添加劑B為陰離子聚合物且當藉由粒徑篩析層析法量測時,具有約150,000至約1,000,000道爾頓、更典型地約300,000至約800,000、最典型地約500,000至約700,000道爾頓之典型重量平均分子量。添加劑B在造紙系統中之效能可高度依賴於陰離子聚合物之分子量及電荷密度。如實例中所展現,除用於本發明之陰離子之外,具有高分子量之添加劑傾向於在所得紙類中產生較差拉伸強度。添加劑B之一個典型適用實例為Hercobond™ 2800乾強度添加劑(丙烯醯胺及丙烯酸之共聚物,可購自Solenis LLC, Wilmington, Del.)其係在pH約為6下具有約-5000至約-6000 ueq/g電荷密度及約600,000至約700,000道爾頓之重量平均分子量之聚合物。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
添加劑A及B可同時或依序添加於濕端中。為同時添加,可同時但經由分離添加點將兩種添加劑引入至濕端中,以免在添加之前將兩種添加劑組合。添加點將視造紙情況而定且因此可以造紙方法中之不同序列或位置添加。一種或兩種添加劑之添加可分開且在濕端造紙系統中之不同添加點處添加。在一典型實施例中,填料首先與紙漿漿料摻合,接著添加添加劑A,隨後添加劑B。可替代添加點及流程可經實施,包括在添加劑A之前添加添加劑B。添加劑A及B兩者在以全部量添加時及在以一系列部分量添加時,添加劑A及B之所有添加順序在此明確地預期用於本文中。
可視針對既定應用之所需紙特性而定以各種劑量添加添加劑A及B。在一個典型實施例中,以乾重計以約1至約60 lbs/公噸之纖維素纖維,典型地約10至約50及更典型地約20至約40 lbs/公噸之量添加(例如,給與)添加劑A。在其他實施例中,以乾纖維素纖維之量計以約0.5至約30 lbs/公噸,典型地約1至約25及更典型地約2至約10之量將添加劑B給與至濕端。以添加劑之乾聚合物含量計,添加劑A與添加劑B的比率可為約2:1至約20:1重量%,典型地約4:1至約15:1,更典型地約4:1至約10:1。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
以乾重計,填料與紙漿配料的比率可為約25:100至約150:100重量%,或為達成紙類灰分含量所需之填料劑量為約5%至約60%,典型地約10%至約50%及最典型地約25%至約45%。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。額外實施例:
在其他實施例中,本發明提供一種製造具有改良的不透明性及改良的填料保留性之紙類的方法。典型地,如熟習此項技術者將理解,該方法可產生具有較高不透明性及較高填料保留性之紙類。該方法包括以下步驟:將添加劑A及添加劑B添加至造紙機之濕端中的漿料中,其中該漿料包括紙漿及添加劑。添加劑A為濕強度劑。添加劑B為陰離子聚合物,在pH約為6之緩衝液中量測時,以乾重計,該陰離子聚合物具有約-3000至約-7000 ueq/g之電荷密度。此外,添加劑B具有約150,000至約1,000,000道爾頓之重量平均分子量。添加劑A及/或B可為如上文所描述之任一者。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
在此等實施例中,不透明性及填料保留性可為如上文所描述。舉例而言,如藉由Technidyne Brightimeter TAPPI方法T425所量測,紙類可具有至少約80%、85%、90%或95%之不透明性。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
如藉由所製備紙張之灰分分析所測定,填料保留性可描述為以保留於最終紙張中之給與填料顆粒之量計之量測值。在各種實施例中,填料保留性值為約36.7% (亦即,來自藉由約21.25 g二氧化鈦(乾)及14.157 g紙漿(乾)製備之紙張大約22%紙張灰分含量)至約95% (亦即,來自藉由約12 g二氧化鈦(乾)及14.157 g紙漿(乾)製備之紙張之大約43.45%紙張灰分含量)。可經由TAPPI方法T413 om-11在900℃下測定灰分含量。保留性可藉由用量測的灰分含量除以理論灰分含量計算,該理論灰分含量係藉由用給與二氧化鈦(以乾重計)除以給與二氧化鈦及紙漿纖維之總和(以乾重計)計算的。在其他實施例中,如上文所描述測定,填料保留性值為約15至約95%、約20至約90%、約25至約85%、約30至約80%、約35至約75%、約40至約70%、約45至約65%、約50至約60%或約55至約60%。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
在各種實施例中,添加劑A選自三聚氰胺甲醛、脲甲醛、乙醛酸化聚丙烯醯胺、聚醯胺基胺環氧氯丙烷及其組合。在其他實施例中,添加劑A包括或為聚醯胺基胺環氧氯丙烷。
在其他實施例中,填料選自二氧化鈦、高嶺土、碳酸鈣、顏料、染料及其組合。填料可為二氧化鈦。舉例而言,二氧化鈦可為銳鈦礦及/或金紅石類型。在其他實施例中,紙類為裝飾或層壓物等級紙類。又另外,在pH約為6量測下,以乾重計,添加劑B之電荷密度可為約-4000至約-6000 ueq/g。另外,添加劑B之重量平均分子量可為約300,000至約800,000道爾頓。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
在另其他實施例中,添加物B為或包括丙烯醯胺、甲基丙烯醯胺或乙基丙烯醯胺中之至少一者與至少一種陰離子單體之反應產物的陰離子聚丙烯醯胺,該至少一種陰離子單體選自丙烯酸、甲基丙烯酸、丙烯酸酯、丙烯酸鹽、伊康酸、反丁烯二酸、丁烯酸、甲基順丁烯二酸、順丁烯二酸及其鹽、2-丙烯醯胺基-2-甲基丙烷磺酸、2-醯基醯胺基-2-甲基丙烷磺酸、苯乙烯磺酸、乙烯基磺酸、N-乙烯吡咯啶酮、N,N-二烯丙基甲基丙烯醯胺、甲基丙烯酸羥基烷酯、N-乙烯基甲醯胺及其組合。在一個實施例中,添加劑B為或包括陰離子共聚物,該陰離子共聚物包含丙烯醯胺與丙烯酸之反應產物。在另一實施例中,添加劑B為或包括陰離子聚合物,該陰離子聚合物包含聚乙烯醇或陰離子官能化聚乙烯醇。在又另一實施例中,添加劑B為或包括第一單體與至少一種陰離子單體之反應產物,該至少一種陰離子單體選自丙烯酸、甲基丙烯酸、丙烯酸酯、丙烯酸鹽、伊康酸、反丁烯二酸、丁烯酸、甲基順丁烯二酸、順丁烯二酸及其鹽、2-丙烯醯胺基-2-甲基丙烷磺酸、2-醯基醯胺基-2-甲基丙烷磺酸、苯乙烯磺酸、乙烯基磺酸、N-乙烯吡咯啶酮、N,N-二烯丙基甲基丙烯醯胺、甲基丙烯酸羥基烷酯、N-乙烯基甲醯胺及其組合。
在其他實施例中,漿料包括纖維素纖維作為紙漿且以約1至約60 lbs/公噸乾纖維素纖維之量添加添加劑A。可替代地,漿料可包括纖維素纖維作為紙漿且以約0.5至約30 lbs/公噸乾纖維素纖維之量添加添加劑B。另外,以乾重計,添加劑A與添加劑B之重量比可為約2:1至約20:1。可替代地,添加劑A與添加劑B之重量比可為約4:1至約15:1。在其他實施例中,漿料包括填料及紙漿且以乾重計,填料與紙漿之比率為約25:100至約150:100重量%。在其他實施例中,紙類具有約5重量%至約60重量%之灰分含量。在甚至其他實施例中,在pH約為6之量測下,以乾重計,添加劑B之電荷密度為約-5000至約-5500 ueq/g,添加劑B之重量平均分子量為約500,000至約700,000道爾頓,漿料包括纖維素纖維,以約20至約40 lbs/公噸乾纖維素纖維之量添加添加劑A,以約1至約20 lbs/公噸乾纖維素纖維之量添加添加劑B,以及紙類具有約25重量%至約40重量%之灰分含量。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
在其他實施例中,相較於僅添加濕強度樹脂,添加添加劑A及添加劑B提供改良的不透明性、填料保留性及/或濕拉伸強度。在一個實施例中,在添加劑B之前將添加劑A添加至造紙漿料中。在另一實施例中,將添加劑A及添加劑B同時添加至造紙漿料中。在另一實施例中,在添加劑A之前將添加劑B添加至造紙漿料中。在再一實施例中,在造紙方法中之一或多個位置處添加添加劑A。可替代地,可在造紙方法中之一或多個位置處添加添加劑B。
在另一實施例中,在pH約為6下量測,以乾重計,添加劑B之電荷密度為約-5000至約-5500 ueq/g。在另一實施例中,添加劑B之重量平均分子量為約500,000至約700,000道爾頓。在再一實施例中,可為此項技術中已知之任一者之第一單體與至少一種陰離子單體反應,該至少一種陰離子單體選自丙烯酸、甲基丙烯酸、丙烯酸酯、丙烯酸鹽、伊康酸、反丁烯二酸、丁烯酸、甲基順丁烯二酸、順丁烯二酸及其鹽、2-丙烯醯胺基-2-甲基丙烷磺酸、2-醯基醯胺基-2-甲基丙烷磺酸、苯乙烯磺酸、乙烯基磺酸、N-乙烯吡咯啶酮、N,N-二烯丙基甲基丙烯醯胺、甲基丙烯酸羥基烷酯、N-乙烯基甲醯胺及其組合。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
在其他實施例中,以約10至約50 lbs/公噸乾纖維素纖維之量添加添加劑A。可替代地,以約20至約40 lbs/公噸乾纖維素纖維之量添加添加劑A。在其他實施例中,以約1至約20 lbs/公噸乾纖維素纖維之量添加添加劑B。可替代地,以約1至約25 lbs/公噸乾纖維素纖維之量添加添加劑B。另外,添加劑A與添加劑B之重量比可為約4:1至約10:1。此外,紙類具有約10重量%至約50重量%之灰分含量。可替代地,紙類可具有約25重量%至約40重量%之灰分含量。在各種非限制性實施例中,所有值及值範圍(整數及分數兩者,包括上述彼等者及在上述彼等者之間)在此明確地預期用於本文中。
在另其他實施例中,相較於僅添加濕強度樹脂,本發明方法中之添加添加劑A及添加劑B提供改良的不透明性、保留性及濕拉伸強度。
在各種實施例中,本文所描述之所有方法步驟及所有化合物之所有組合明確地預期用於本文中,即使彼等方法步驟及/或化合物未描述於上文之相同或類似段及/或上文分組在一起。實例
實驗室實驗係藉由在Noble & Wood手抄紙模具上製造手抄紙完成的。紙張藉由將30%二氧化鈦(R-796+, Chemours, Wilmington, Del.)添加至精煉至大約300 mL Canadian Standard Freeness之1%桉紙漿來製備,其中漿料經調節至pH 9。以0.85 g乾填料形式將填料添加至g乾紙漿。隨後藉由稀釋硫酸將系統pH調節至大約6。隨後在手抄紙模具上製造紙張而無需回收白水。將化學添加劑添加至紙漿/填料漿料中伴隨頂置式攪拌。所使用PAE樹脂為KymeneTM
XRV20 (Solenis LLC, Wilmington, Del.),其經稀釋為標準硬度及鹼度之1%水溶液且pH經調節至6。各種陰離子添加劑經研究且在特定實例中經標記。隨後將紙漿漿料添加至設備之比例調節器中且紙張形成。以60 psi按壓濕紙張且隨後在大約115℃下用滾筒乾燥器(drum dryer)乾燥。滾筒乾燥器係以將紙張暴露於乾表面持續35至40秒之方式操作。
將所得手抄紙在具有受控溫度及濕度之房間中老化持續至少2週。調節情況為藉由TAPPI方法T 402概述之彼等情況且房間經控制在50% +/- 2%相對濕度及23℃ +/- 1.0℃溫度下。灰分含量係使用TAPPI T413 om-11方法在900℃下量測的。保留性%係以所使用紙漿量及所添加填料量計藉由用量測灰分含量除以理論灰分含量計算的。不透明性係使用Technidyne Brightimeter量測的。將紙張置放於透明塑膠袋中且不透明性係首先在乾紙張上量測且隨後再次在浸沒在植物油(大豆油) (可購自更佳Living Brands LLC,Pleasanton,CA)中之紙張上量測。油浸泡步驟自紙張中移除空氣且使孔與最終層壓產物不透明性相關。濕拉伸強度係使用TAPPI方法456以及1"測試條、5"標距及速率為1 in/min量測的。基本重量係藉由稱重自手抄紙切割之7"×7"之質量來量測的。
陰離子聚丙烯醯胺系統經特徵為分子量及電荷密度兩者。對於電荷密度量測,使用Mütek PCD-05顆粒電荷偵測器。在去離子水中將陰離子聚丙烯醯胺樣品稀釋至大約0.04重量%,隨後將2mL此溶液添加至含pH 6之8 mL 0.01M磷酸酯緩衝液之Mütek量測單元中。藉由氯化聚二烯丙基二甲基銨(「聚DADMAC」)滴定樣品直至量測到0 mV之串流電位。報導值係以聚合物之乾重計。
陰離子聚丙烯醯胺分子量係使用粒徑篩析層析法在以下情況下測定:
移動相:0.1 M硝酸鈉/20%乙腈
流動速率:0.8 ml/min
管柱:串聯2 TSKgel GMPWxl
管柱溫度:40℃
DRI偵測器溫度:40℃
校準:相對於聚(丙烯酸)鈉鹽,窄分子量標準
樣品濃度:典型地2 mg/ml移動相
樣品製備:在移動相中攪拌1至2小時。
過濾:0.45 μm PVDF針筒過濾器。
各種陰離子聚丙烯醯胺添加劑之特性展示於表1中。添加劑B1至B9為具有各種電荷密度及分子量之陰離子聚丙烯醯胺。添加劑B1、B3、B4及B5為可購自Solenis LLC, Wilmington, Del之商業樣品。添加劑B2為藉由25莫耳%丙烯酸調配之丙烯醯胺及丙烯酸共聚物之實驗室樣品。FLOPAM™ AN 905, FLOPAM™ AN 956 SH及FLOPAM™ AN 995 SH為可購自SNF Inc, Riceboro, GA之習知陰離子保留性助劑。Chemtall™ AN 956 VLM亦為可購自Chemtall, Riceboro, GA之習知陰離子保留性助劑。表 1 實例 1 ( 添加劑 A 單獨 )
出於比較目的,紙張係藉由各種濕強度劑量(以乾纖維計0%至3%)下之Kymene™ XRV20濕強度樹脂(PAE樹脂)作為添加劑A單獨製造的。紙類特性展示於表2中。表 2 表 2 ( 對照 )
PAE樹脂之存在首先改良保留性優於無添加劑之紙張之保留性。然而,在更高PAE樹脂添加水準下,保留性及不透明性因存在額外PAE樹脂而降低。濕拉伸強度隨著PAE劑量逐漸增加而持續增大。實例 2
在PAE樹脂添加後,以乾重計,以2:1重量%之添加劑A與添加劑B之比率添加添加劑B1(陰離子聚丙烯醯胺)。紙類特性展示於表3中。表 3 表 3 ( 對照 )
造紙方法中之添加劑A及B之組合提供比添加劑A單獨優良得多的保留性。此亦產生改良的不透明性值。亦優於所有添加劑A劑量改良濕拉伸強度尖峰負載,其指示未歸因於提高的保留性而產生負面影響。保留性、不透明性及濕尖峰負載展示優於比較例1中展示的對應PAE劑量結果之改良。實例 3
為了比較,若干種陰離子添加劑測試於該模型中。標準陰離子聚丙烯醯胺保留性助劑結合添加劑A (KymeneTM
XRV20)用作對照組。此等經標記為添加劑B6、B7、B8及B9。全部四種保留性助劑具有比實例2中所使用之添加劑B高得多的分子量。在添加添加劑A後應用全部且以乾重計以10:1重量%之添加劑A與添加劑B之比率。針對添加劑A單獨(無添加劑B)之紙類結果展示於表4中。表 4 表 4 ( 對照 )
針對添加劑A加上各種比較性添加劑B(標準陰離子聚丙烯醯胺保留性助劑)之結果展示於表5中。表 5 表 5 ( 對照 )
結果展示就不透明性及保留性而言在添加劑A單獨時之類似改良,但濕拉伸尖峰負載小於添加劑A單獨之情況中所獲得之濕拉伸尖峰負載(表4及5之比較)。較高分子量添加劑B系統之存在產生較差濕及乾強度特性。不希望受理論所束縛,高分子量陰離子聚丙烯醯胺產生較不良紙類形成,其產生可能歸因於填料顆粒之過度絮凝之較低強度特性,進而破壞對於拉伸強度而言重要的纖維與纖維結合。實例 4
在此評估中,本發明內之添加劑B系統係以與表5、實例3中經測試之陰離子聚丙烯醯胺保留性助劑相同之劑量經測試。添加劑A為KymeneTM
XRV20。劑量水準以乾聚合物計為10:1重量%之添加劑A與添加劑B。結果報導為在相同添加劑A劑量下藉由添加劑A單獨進行獲得之紙張特性百分比。結果展示於表6中。表 6
在此表中顯而易見應用添加劑B2、B3、B4及B5系統展示優於添加劑A情況單獨之更佳保留性改良且比在更高添加劑A添加水準下之習知保留性助劑(添加劑B6、B7、B8及B9)更大的保留性改良。此亦翻譯為當相較於習知保留性助劑時,在2及3%添加劑A添加水準下之更高不透明性水準。在濕拉伸尖峰負載價值中觀測到最大效能改良。結果展示添加劑B2、B3、B4及B5產生優於添加劑A單獨情況之改良,然而使用習知保留性助劑之彼等展示小於添加劑A單獨之尖峰負載。添加劑B6、B7、B8及B9對於濕拉伸強度具有負面影響。
預期在各種非限制性實施例中,前述化合物、組分、重量百分比、方法步驟等之全部組合可與彼此一起使用,即使未描述於相同或類似段落中亦如此。換言之,所有前述組合在此明確地預期用於各種非限制性實施例。
儘管前述詳細描述中已呈現至少一個例示性實施例,但應瞭解存在大量變體。亦應瞭解,一或多個例示性實施例僅為實例,且不意欲以任何方式限制範疇、適用性或組態。確切而言,前述詳細描述將為熟習此項技術者提供用於實施例示性實施例之便利路線圖。應理解,在不背離所附申請專利範圍中闡述之範疇的情況下,可對描述於例示性實施例中之元素之功能及配置進行各種改變。
Claims (10)
- 一種製造具有不透明性及填料保留性之紙類的方法,該方法包含以下步驟:將添加劑A及添加劑B添加至造紙機之濕端中之漿料中,其中該漿料包含紙漿及填料;其中添加劑A為濕強度劑;其中添加劑B為陰離子聚合物,當在pH約為6之緩衝液中量測時,以乾重計,該陰離子聚合物具有約-3000至約-7000ueq/g之電荷密度;且其中添加劑B具有約150,000至約1,000,000道爾頓之重量平均分子量;及其中添加劑B為包含丙烯醯胺、甲基丙烯醯胺或乙基丙烯醯胺中之至少一者與至少一種陰離子單體之反應產物的陰離子聚丙烯醯胺,該至少一種陰離子單體選自丙烯酸、甲基丙烯酸、丙烯酸酯、丙烯酸鹽、伊康酸、反丁烯二酸、丁烯酸、甲基順丁烯二酸、順丁烯二酸及其鹽、2-丙烯醯胺基-2-甲基丙烷磺酸、2-醯基醯胺基-2-甲基丙烷磺酸、苯乙烯磺酸、乙烯基磺酸、N-乙烯吡咯啶酮、N,N-二烯丙基甲基丙烯醯胺、甲基丙烯酸羥基烷酯、N-乙烯基甲醯胺及其組合。
- 如請求項1之方法,其中添加劑A選自三聚氰胺甲醛、脲甲醛、乙醛酸化聚丙烯醯胺、聚醯胺基胺環氧氯丙烷及其組合。
- 如請求項1之方法,其中添加劑A包含聚醯胺基胺環氧氯丙烷。
- 如請求項1之方法,其中該填料為二氧化鈦。
- 如請求項1至4中任一項之方法,其中以乾重計,在pH約為6下量測的添加劑B之電荷密度為約-4000至約-6000ueq/g。
- 如請求項1至4中任一項之方法,其中添加劑B之重量平均分子量為約300,000至約800,000道爾頓。
- 如請求項1至4中任一項之方法,其中添加劑B包含陰離子共聚物,該陰離子共聚物包含丙烯醯胺與丙烯酸之反應產物。
- 如請求項1至4中任一項之方法,其中以乾重計,添加劑A與添加劑B之重量比為約2:1至約20:1。
- 如請求項1至4中任一項之方法,其中以乾重計,在pH約為6下量測之添加劑B之電荷密度為約-5000至約-5500ueq/g;其中添加劑B之重量平均分子量為約500,000至約700,000道爾頓,其中該漿料包含纖維素纖維,其中以約20至約40 lbs/公噸乾纖維素纖維之量添加劑A,其中以約1至約20 lbs/公噸乾纖維素纖維之量添加添加劑B,且其中該紙類具有約25至約40重量%之灰分(ash)含量。
- 如請求項1至4中任一項之方法,其中添加劑A為聚醯胺基胺環氧氯丙烷,其中添加劑B為聚丙烯醯胺,其為丙烯醯胺與丙烯酸之反應產物且具 有173,000至646,000g/mol之重量平均分子量,且其中該漿料包含少於5重量%之添加劑,該添加劑不為添加劑A或添加劑B或填料。
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2020
- 2020-07-15 CL CL2020001876A patent/CL2020001876A1/es unknown
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US20050155731A1 (en) * | 2003-10-24 | 2005-07-21 | Martin William C. | Process for making abrasion resistant paper and paper and paper products made by the process |
TW201516212A (zh) * | 2013-09-12 | 2015-05-01 | Ecolab Usa Inc | 造紙方法及組成物 |
CN106062275A (zh) * | 2013-12-30 | 2016-10-26 | 凯米罗总公司 | 一种用于提供预处理过的填料组合物的方法及其在纸和纸板制造中的用途 |
CN105696414A (zh) * | 2014-11-27 | 2016-06-22 | 艺康美国股份有限公司 | 造纸助剂组合物以及提高纸张抗张强度的方法 |
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RU2020126586A (ru) | 2022-02-17 |
US20190218718A1 (en) | 2019-07-18 |
FI3740613T3 (fi) | 2023-09-14 |
EP3740613A1 (en) | 2020-11-25 |
MX2020007581A (es) | 2020-09-03 |
AU2019209164A1 (en) | 2020-08-27 |
KR20200104408A (ko) | 2020-09-03 |
CN111615572A (zh) | 2020-09-01 |
AU2019209164B2 (en) | 2022-12-08 |
EP3740613B1 (en) | 2023-07-26 |
BR112020014434A2 (pt) | 2020-12-01 |
TW201937043A (zh) | 2019-09-16 |
ES2954570T3 (es) | 2023-11-23 |
EP3740613A4 (en) | 2021-10-27 |
RU2020126586A3 (zh) | 2022-03-21 |
CL2020001876A1 (es) | 2020-12-11 |
US10975524B2 (en) | 2021-04-13 |
WO2019143519A1 (en) | 2019-07-25 |
CA3088175A1 (en) | 2019-07-25 |
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