TW201942444A - Pulp and lyocell articles with reduced cellulose content - Google Patents
Pulp and lyocell articles with reduced cellulose content Download PDFInfo
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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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/02—Synthetic cellulose fibres
- D21H13/08—Synthetic cellulose fibres from regenerated cellulose
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
- D01F2/30—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate by the dry spinning process
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
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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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
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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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
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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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/02—Synthetic cellulose fibres
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- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Textile Engineering (AREA)
- Paper (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
- Knitting Of Fabric (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
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Abstract
Description
本發明描述能大規模穩定製造具有降低的纖維素含量的萊纖纖維之特殊纖維素組合物,以及由彼製造的萊纖纖維。The present invention describes a special cellulose composition capable of stably producing Lycium fiber with reduced cellulose content on a large scale, and Lycium fiber made from it.
萊纖纖維用於各種應用。經純化的纖維素經常用作原料,具有非常小比例由纖維素製成的不同最終部分。Lycra fibers are used in a variety of applications. Purified cellulose is often used as a raw material, with very small proportions of different final parts made from cellulose.
木漿得自僅由40至44重量%纖維素所組成的木材。由於用於製造萊纖模製品的木漿中一般需要超過95重量%的高纖維素含量,因此供資材用途用的原料將於蒸煮及漂白期間流失大部分。無論是在從木材到木漿或者是到該萊纖最終產品的木漿製造過程中,皆有許多已知的降低半纖維素比例的方式:
a) 消化:大部分半纖維素在亞硫酸鹽蒸煮時流失,而於鹼性消化時則在蒸煮之前利用預水解作用(prehydrolysis)除去半纖維素。
b) 漂白:通常用於消除殘留的木質素及/或光學增白,但是也破壞了半纖維素組分
c) 支鏈半纖維素部分於該萊纖溶劑中的部分不溶性
d) 於紡絲原液中降解,其後於紡絲浴中溶解。Wood pulp is obtained from wood consisting of only 40 to 44% by weight cellulose. As wood pulp used in the manufacture of nylon fiber molded products generally requires a high cellulose content of more than 95% by weight, the raw materials used for funding materials will lose most of them during cooking and bleaching. There are many known ways to reduce the hemicellulose ratio, whether it is from wood to wood pulp or to the production of the final fiber pulp:
a) Digestion: Most hemicellulose is lost during sulfite cooking, while in alkaline digestion, hemicellulose is removed by prehydrolysis before cooking.
b) Bleaching: Usually used to remove residual lignin and / or optical whitening, but also destroys the hemicellulose component
c) Partial insolubility of the branched hemicellulose part in the fiber solvent
d) Degraded in the spinning dope and then dissolved in the spinning bath.
確實有人很努力把這些其他組分當成副產物。但是,由於已知的技術限制,僅少數實施。在來自木漿製造的廢液中,除了與強酸或鹼混合以外,這些另外的木材組分以大量不同降解產物的形式存在,這使得分離及進一步加工非常困難。WO 98/16682描述適用於纖維製造的纖維素組合物之製造方法。將咸認為不適合纖維製造(而是僅用於紙張製造)的起始混合物加工以使該半纖維素含量,特別是該木聚醣含量,降低。WO 99/47733描述許多萊纖纖維而且WO 2010/132151 A2揭露一種具有低聚合度纖維素的木漿。There are indeed efforts to treat these other components as by-products. However, due to known technical limitations, only a few have been implemented. In waste liquor from wood pulp manufacture, in addition to being mixed with strong acids or alkalis, these additional wood components are present in the form of a large number of different degradation products, which makes separation and further processing very difficult. WO 98/16682 describes a method for producing a cellulose composition suitable for use in the manufacture of fibers. The starting mixture, which is deemed unsuitable for fiber manufacturing (but only for paper manufacturing), is processed to reduce the hemicellulose content, especially the xylan content. WO 99/47733 describes many lyocell fibers and WO 2010/132151 A2 discloses a wood pulp with a low degree of polymerization of cellulose.
然而,近年來有人努力通過使用具有增量的木質素及/或半纖維素之纖維素來拓寬萊纖產物的原料基礎。US 6440523和US 6444314描述這樣的方法作為實例:However, in recent years, efforts have been made to broaden the raw material base of Lycra fiber products by using cellulose with incremental lignin and / or hemicellulose. US 6440523 and US 6444314 describe such methods as examples:
在這些論文中採用的方法基本上是在描述木漿及/或由彼製成的萊纖產物,其除了該纖維素含量之外也具有高於5重量%的半纖維素含量。然而,咸認為所有這些著作中必不可少的是,只有在同時滿足許多其他基本條件的情況下才能實現所描述的較高半纖維素含量。這些是,舉例來說,該木漿的一定黏度、最大銅價(copper number)及/或最大K值(kappa number)。The method used in these papers is basically describing wood pulp and / or lye fiber products made therefrom, which in addition to this cellulose content also has a hemicellulose content of more than 5% by weight. However, Xian believes that in all of these works, the higher hemicellulose content described can be achieved only if many other basic conditions are met at the same time. These are, for example, a certain viscosity of the wood pulp, a maximum copper number and / or a maximum k number.
儘管這些論文中有描述萊纖產物,但是值得注意的是,基於這些智慧財產權的發展尚未被大規模實現,然而特地使用具有較高半纖維素含量的纖維素會帶來顯著的成本及從而競爭力的優勢。這可能是由於難以從實驗室規模及可實現的纖維性質擴大,這不符合紡織及非織物市場的預期。US 2015/0184338 A1揭露具有低含量半纖維素的木漿。
本發明的任務Although Lycra products are described in these papers, it is worth noting that the development based on these intellectual property rights has not been achieved on a large scale. However, the special use of cellulose with a higher hemicellulose content will bring significant costs and thus competition. Strength advantage. This may be due to the difficulty in expanding from laboratory scale and achievable fiber properties, which is not in line with expectations in the textile and non-woven markets. US 2015/0184338 A1 discloses wood pulp with a low content of hemicellulose.
The task of the invention
為了最大限度地利用資源,吾人所欲為能從該原料木材中利用盡可能多的材料組分來製造萊纖纖維。尋求最全面的可持續性及真正有效的生物精煉(biorefinery)概念的主要目標必須是從一開始就盡可能為主要產品,換言之萊纖成形體,全面地使用天然原料木材。副產品的萃取仍然非常重要,但是總體而言這仍然是次要的。先前為達此目的所做的努力已經失敗,因為纖維中的纖維素含量降低導致所得的(萊纖)纖維(或模製體的其他變體)之材料和性質參數的巨大變化,或者另一方面,無法做到穩定的大規模生產。相反地,大量專利及公開要求木質素、半纖維素及附屬組分的含量對於於萊纖法中大規模應用化學木漿而言應該極低。In order to maximize the use of resources, I want to be able to use as many material components as possible from this raw wood to make fiber. The main goal in the search for the most comprehensive sustainability and truly effective concept of biorefinery must be from the beginning as much as possible the main product, in other words the fiber-formed body, using wood from natural raw materials in a comprehensive way. Extraction of by-products is still very important, but overall it remains secondary. Previous efforts to achieve this have failed because the reduced cellulose content in the fiber caused a drastic change in the material and property parameters of the resulting (rayon) fiber (or other variant of the molded body), or another On the other hand, stable large-scale production cannot be achieved. On the contrary, a large number of patents and publications require that the content of lignin, hemicellulose and auxiliary components should be extremely low for the large-scale application of chemical wood pulp in the Lycra method.
由於這些原因,吾人所欲為提供可大規模使用的技術,其藉由提昇其他木材組分,特別是半纖維素,還有木質素的比例來降低纖維成品中纖維素的比例,而對得到的材料參數沒有重大限制。儘管有許多最先進的方法,但是目前還沒有已知的方法可以大規模地用於製造此具有降低的纖維素含量之萊纖產物。For these reasons, what I want to provide is a technology that can be used on a large scale. By increasing the proportion of other wood components, especially hemicellulose and lignin, to reduce the proportion of cellulose in the finished fiber, There are no major restrictions on the material parameters. Although there are many state-of-the-art methods, there is currently no known method that can be used on a large scale to make this fiber product with reduced cellulose content.
本發明克服了上述先前技藝的問題。本發明提供如申請專利範圍第1項之木漿、如申請專利範圍第9項之萊纖產物及如申請專利範圍第16和18項之方法。於附屬項及以下本發明的詳細說明中指明本發明的較佳形式。The present invention overcomes the problems of the aforementioned prior art. The present invention provides a wood pulp such as those in the scope of the patent application, a fiber product such as the scope of the patent application, and a method in the scope of the patent application. The preferred forms of the invention are specified in the appended items and the following detailed description of the invention.
特別地,本發明提供以下態樣,以及附件項及說明書所引用的較佳具體實例。
1. 一種適用於製造萊纖成型體之木漿,其具有90重量%或更低的纖維素含量,較佳為85重量%或更低,及至少7重量%的半纖維素含量,該木漿之特徵在於,存於該半纖維素中的C5/木聚醣與C6/甘露聚醣部分的比率(C5/C6比率)係於125:1至1:3的範圍中。
2. 如具體實例1之纖維素,其中該C5/C6比率係於25:1至1:2的範圍中。
3. 如具體實例1及/或2之木漿,其中該半纖維素的比例為10重量%或更高。
4. 如上述具體實例中至少一項之木漿,其半纖維素係以天然狀態存在,已經藉由加工製程進行化學改質,或已經以單獨製程步驟進行化學改質或官能化。
5. 如上述具體實例中至少一項之木漿,其具有高於1重量%的木質素含量。
6. 如上述具體實例中至少一項之木漿,其中該纖維素含量係由於來自木材的木質素、附屬成分的存在及/或金屬化合物的添加而進一步降低。
7. 如上述具體實例中至少一項之木漿,其具有9重量%或更高的木聚醣含量及/或6重量%或更高的甘露聚醣含量。
8. 如具體實例7之木漿,其具有9重量%或更高的木聚醣含量及1重量%或更低的甘露聚醣含量。
9. 一種萊纖成形體,其係藉由使用如具體實例1至8中任一項之木漿製備。
10. 如具體實例9之萊纖成形體,其中該成形體係選自纖維、長絲(filament)、短纖維(staple fibre)、非織造針織物、膜及球形粉末。
11. 如具體實例9及/或10中至少一項之萊纖成形體,其中該成形體係纖維、長絲或短纖維,其具有低於90重量%的纖維素含量、高於5重量%的半纖維素含量及125:1至1:3,較佳為25:1至1:2的C5/C6比率。
12. 如具體實例9至11中至少一項之萊纖成形體,其中該半纖維素含量係高於10重量%。
13. 如具體實例9至12中至少一項之萊纖成形體,其中該成形體係具有高於70%,較佳為高於75%,特別是高於80%的WRV之纖維、長絲或短纖維。
14. 如具體實例9至13中至少一項之萊纖成形體,其中該成形體具有40%或更低的結晶度。
15. 如具體實例9至14中至少一項之萊纖成形體,其具有高於0重量%至5重量%的木質素含量。
16. 一種製造萊纖成形體之方法,其包含將具有90重量%或更低,更佳為85重量%或更低的纖維素含量及至少7重量%的半纖維素含量之木漿溶解,其特徵在於合適的溶劑中,存於該半纖維素中的C5/木聚醣與C6/甘露聚醣的比率(C5/C6比率)係於125:1至1:3的範圍中,並且將溶液形成為萊纖成形體。
17. 如具體實例16之方法,其中該萊纖成形體係藉由萊纖紡絲製程獲得。
18. 一種製造如具體實例1至8中任一項之木漿之方法,前述方法包含以下步驟中的至少其一:
a) 將純木漿與木聚醣及/或甘露聚醣混合;
b) 藉由化學及/或物理方法處理具有包括甘露聚醣在內的半纖維素含量之木漿以改變彼內所含的半纖維素含量及/或半纖維素組成;
c) 使用針葉及/或落葉木材製造木漿;
d) 將不含甘露聚醣的木漿與富含半纖維素的木漿混合,並且視需要地於其後對該混合物進行化學及/或物理處理以調節該半纖維素含量及/或該半纖維素部分的組成;
e) 混合二具有不同半纖維素含量及/或半纖維素組成的木漿,並且視需要地於其後對該混合物進行化學及/或物理處理以調節該半纖維素含量及/或該半纖維素部分的組成。
19. 如具體實例18之方法,其中不同的木漿係選自以硬木及軟木為底質的木漿。In particular, the present invention provides the following aspects, as well as preferred specific examples cited in the attached items and the description.
1. A wood pulp suitable for manufacturing a fiber-formed body, having a cellulose content of 90% by weight or less, preferably 85% by weight or less, and a hemicellulose content of at least 7% by weight, the wood The pulp is characterized in that the ratio of C5 / xylan to C6 / mannan moiety (C5 / C6 ratio) existing in the hemicellulose is in a range of 125: 1 to 1: 3.
2. The cellulose of specific example 1, wherein the C5 / C6 ratio is in the range of 25: 1 to 1: 2.
3. The wood pulp according to the specific examples 1 and / or 2, wherein the proportion of the hemicellulose is 10% by weight or more.
4. The hemicellulose of at least one of the above specific examples exists in a natural state, has been chemically modified through a processing process, or has been chemically modified or functionalized in a separate process step.
5. The wood pulp according to at least one of the above specific examples, which has a lignin content higher than 1% by weight.
6. The wood pulp according to at least one of the above specific examples, wherein the cellulose content is further reduced due to the presence of lignin, ancillary components and / or addition of metal compounds from the wood.
7. The wood pulp according to at least one of the above specific examples, which has a xylan content of 9% by weight or more and / or a mannan content of 6% by weight or more.
8. The wood pulp of specific example 7, which has a xylan content of 9% by weight or more and a mannan content of 1% by weight or less.
9. A fiber-formed body produced by using a wood pulp as described in any one of specific examples 1 to 8.
10. The lyocell shaped body according to the specific example 9, wherein the forming system is selected from the group consisting of fibers, filaments, staple fibers, nonwoven knits, films, and spherical powders.
11. The lyophilized fiber shaped body according to at least one of the specific examples 9 and / or 10, wherein the forming system fiber, filament or short fiber has a cellulose content of less than 90% by weight and a fiber content of more than 5% by weight Hemicellulose content and a C5 / C6 ratio of 125: 1 to 1: 3, preferably 25: 1 to 1: 2.
12. The fiber-reinforced molded article according to at least one of the specific examples 9 to 11, wherein the hemicellulose content is higher than 10% by weight.
13. The fiber-formed article according to at least one of the specific examples 9 to 12, wherein the forming system has a WRV fiber, filament or more than 70%, preferably more than 75%, especially more than 80%. short fibre.
14. The fiber-formed article according to at least one of the specific examples 9 to 13, wherein the formed article has a crystallinity of 40% or less.
15. The lyocell shaped body according to at least one of the specific examples 9 to 14, which has a lignin content higher than 0% to 5% by weight.
16. A method for manufacturing a fiber-formed body, comprising dissolving a wood pulp having a cellulose content of 90% by weight or less, more preferably 85% by weight or less, and a hemicellulose content of at least 7% by weight, It is characterized in that the ratio of C5 / xylan to C6 / mannan (C5 / C6 ratio) stored in the hemicellulose is in a range of 125: 1 to 1: 3 in a suitable solvent, and The solution was formed into a formed fiber.
17. The method according to the specific example 16, wherein the fiber forming system is obtained by a fiber spinning process.
18. A method of manufacturing wood pulp according to any one of the specific examples 1 to 8, the aforementioned method comprises at least one of the following steps:
a) mixing pure wood pulp with xylan and / or mannan;
b) chemically and / or physically treating wood pulp having a hemicellulose content including mannan to change the hemicellulose content and / or hemicellulose composition contained therein;
c) Use of coniferous and / or deciduous wood to make wood pulp;
d) mixing wood pulp without mannan with hemicellulose-rich wood pulp, and optionally chemically and / or physically treating the mixture thereafter to adjust the hemicellulose content and / or The composition of the hemicellulose part;
e) mixing two wood pulps having different hemicellulose content and / or hemicellulose composition, and thereafter chemically and / or physically treating the mixture as necessary to adjust the hemicellulose content and / or the hemicellulose Composition of cellulose part.
19. The method of embodiment 18, wherein the different wood pulps are selected from wood pulps with hardwood and softwood as substrates.
若該纖維素的比例於萊纖製程時降低了,這意指節省的部分將被該木材原料中的其他物質抵消。如上所述,當該纖維素含量降低時,這會帶來製程穩定性或性質變化的問題。該原料木材中非纖維素材料的主要組分是半纖維素(基本上為選自糖單體木糖、阿拉伯糖、甘露糖、半乳糖、葡萄糖及鼠李糖的多醣)、木質素及附屬成分。If the proportion of cellulose is reduced during the processing of Lycra, this means that the savings will be offset by other substances in the wood raw material. As mentioned above, when the cellulose content is reduced, this brings problems of process stability or property change. The main component of the non-cellulosic material in the raw wood is hemicellulose (basically a polysaccharide selected from the sugar monomers xylose, arabinose, mannose, galactose, glucose and rhamnose), lignin and ancillary ingredient.
纖維素:其係木材細胞壁的結構物質,主要用於拉伸強度。葡萄糖單元的長分子鏈依數倍於螺旋結構的所謂原纖維(fibril)之形式儲存在一起。此細胞壁中的螺旋排列確保樹木的良好彎曲強度,例如於風載荷的情況或於例如屋頂建築的木材的情況。纖維素是親水性的,但是由於其高結晶度而不是水溶性的。Cellulose: It is a structural material of the wood cell wall, mainly used for tensile strength. The long molecular chains of glucose units are stored together in the form of so-called fibrils, which are multiples of the helical structure. This helical arrangement in the cell wall ensures good bending strength of the tree, such as in the case of wind loads or in the case of, for example, the wood of a roof building. Cellulose is hydrophilic, but not water-soluble due to its high crystallinity.
木質素:用於非晶形基質形式的纖維素之固態黏合的黏合劑。因此,木質素主要負責抗壓強度(compressive strength),另一方面木質素的柔韌性較差,與纖維素相反地是疏水性的。其負責樹木的支承體。不儲存木質素的植物僅達到低生長高度。木質素在生物學上相對穩定並且只能緩慢地生物降解。Lignin: A binder for solid adhesion of cellulose in the form of an amorphous matrix. Therefore, lignin is mainly responsible for compressive strength. On the other hand, lignin has poor flexibility and is hydrophobic in contrast to cellulose. It is responsible for the support of the tree. Plants that do not store lignin only reach low growth heights. Lignin is relatively biologically stable and can only be slowly biodegraded.
半纖維素於本發明中意指以C5及/或C6糖的短鏈聚合物形式存於木材中的組分。與纖維素相比,其具有側基而且因此僅能以更小許多的程度形成晶體。其基本構建單元是甘露糖、木糖、葡萄糖、鼠李糖及半乳糖。該側基較佳地由阿拉伯糖基、乙醯基及半乳糖殘基以及O-乙醯基和4-O-甲基葡醣醛酸側基組成。已知甘露聚醣偏好與纖維素結合,而木聚醣易於與木質素結合。半纖維素的組成根據所用木材的類型而變化很大。在木漿的製造過程中,側鏈被部分分離並且聚合物鏈分裂。在本發明的上下文中,措辭半纖維素包括處於其天然結構的那些以及藉由其加工改變的那些,以及另外藉由特定化學改質調整其預期用途的那些。還包括短鏈纖維素及DP至高500的其他多醣類(polyose)。Hemicellulose in the present invention means a component that is present in wood as a short-chain polymer of C5 and / or C6 sugars. Compared to cellulose, it has pendant groups and can therefore only form crystals to a much smaller extent. The basic building blocks are mannose, xylose, glucose, rhamnose and galactose. The pendant group preferably consists of arabinose, acetamyl, and galactose residues, as well as O-acetamyl and 4-O-methylglucuronic acid side groups. It is known that mannan prefers to bind to cellulose, while xylan easily binds to lignin. The composition of hemicellulose varies greatly depending on the type of wood used. During the manufacture of wood pulp, the side chains are partially separated and the polymer chains are split. In the context of the present invention, the wording hemicellulose includes those in their natural structure and those that are altered by their processing, as well as those that otherwise adjust their intended use by specific chemical modifications. Also included are short-chain cellulose and other polyoses with DP up to 500.
附屬組分:附屬構成成分是木質素、纖維素及半纖維素以外的有機和無機木材組分,而且通常包括鹽及至多約100個原子的低分子有機化合物,例如單寧(tannin)、樹脂、脂肪和蠟、單寧和腐植質、萜烯 、類萜烯化合物(terpenoid)和酚類化合物、果膠、木栓質(suberin)、多酚及多醣。Ancillary components: Ancillary constituents are organic and inorganic wood components other than lignin, cellulose and hemicellulose, and usually include salts and low molecular organic compounds up to about 100 atoms, such as tannin, resin , Fats and waxes, tannins and humics, terpenes, terpenoids and phenols, pectin, suberin, polyphenols and polysaccharides.
若纖維素材料中的纖維素含量按照所需降低並且由原料木材的其他組分來補償此降低,則其驚人地顯示只有特定比率的不同類型糖的組合才有可能顯出某一纖維素,雖然其纖維素含量降低了,卻能安全地大規模製造萊纖產物,從而使這些產品也具有降低的纖維素含量,但是仍然具有令人滿意的產品性能。If the cellulose content in the cellulosic material is reduced as required and this decrease is compensated by other components of the raw wood, it surprisingly shows that only certain combinations of different types of sugars are likely to show a certain cellulose, Although their cellulose content is reduced, they can be safely manufactured on a large scale, so that these products also have a reduced cellulose content, but still have satisfactory product performance.
根據本發明,基本上低於90重量%的木漿中降低的纖維素含量具有至少7重量%的半纖維素含量,具有五碳原子的糖(例如木聚醣)與具有六碳原子的糖(例如甘露聚醣)之比率(以下稱為C5/C6比率)係於125:1至1:3的範圍中。According to the present invention, the reduced cellulose content in substantially less than 90% by weight of wood pulp has a hemicellulose content of at least 7% by weight, sugars having five carbon atoms (such as xylan) and sugars having six carbon atoms The ratio (for example, mannan) (hereinafter referred to as the C5 / C6 ratio) is in the range of 125: 1 to 1: 3.
令人驚訝的是,即使該木漿中的纖維素含量降低,也可用此木漿安全地實現萊纖產物的大規模生產。Surprisingly, even if the content of cellulose in the wood pulp is reduced, the large-scale production of nylon fiber products can be safely achieved with the wood pulp.
此處所用的萊纖材料,本發明的上下文中偏好使用者,如已經說明的那樣,顯示出具有本文定義的組成之相對高含量的半纖維素。與具有低半纖維素含量的標準木漿相比,特別是在現有技術中用於製造標準萊纖纖維,在本發明上下文中使用的較佳木漿也顯示出如下文所列的其他差異。
與標準萊纖材料相比,本發明較佳使用的萊纖材料顯示出相當蓬鬆的外觀。研磨之後(在製造用於製造萊纖製程的紡絲溶液的起始材料期間),這將造成高比例的較大顆粒之粒徑分佈。結果,總體密度(bulk density)比具有低半纖維素含量的標準木漿更低許多。此低總體密度在製造該紡絲溶液的期間必需順應配料參數(例如使用至少二存儲槽配料)。此外,本發明較佳使用的萊纖材料顯示對NMMO的浸漬特性,在此其與標準萊纖材料相比顯示更難以浸漬。這可藉由根據Cobb推估法評估浸漬性質而檢測。儘管標準木漿的Cobb值通常大於2.8 g/g (根據DIN EN ISO 535,順應使用78% NMMO水溶液於75°C下加上2分鐘的浸漬時間而測定),但是本發明較佳使用的木漿卻顯示出約2.3 g/g的Cobb值。這需要於紡絲溶液製備期間進行調整,例如增長的溶解時間(例如WO 94/28214及WO 96/33934中解釋的)及/或溫度適應及/或於溶解期間提高的剪切(例如WO 96/33221、WO 98/05702及WO 94/28217)。這樣便能製造出使得此處所述的木漿能用於標準萊纖紡絲製程之紡絲溶液。The fiber material used herein, which is preferred by the user in the context of the present invention, has, as already explained, a relatively high content of hemicellulose having a composition as defined herein. Compared to standard wood pulps with a low hemicellulose content, and especially in the prior art for the production of standard lycra fibers, the preferred wood pulps used in the context of the present invention also show other differences as listed below.
Compared to standard Lycra materials, the Lycra materials that are preferably used in the present invention exhibit a rather fluffy appearance. After milling (during the manufacture of the starting material for the spinning solution used in the process of making fiber), this will result in a high proportion of the particle size distribution of the larger particles. As a result, the bulk density is much lower than standard wood pulp with a low hemicellulose content. This low overall density must comply with the dosing parameters (eg using at least two storage tank dosing) during the manufacture of the spinning solution. In addition, the nylon fiber material that is preferably used in the present invention exhibits the immersion characteristics to NMMO, and here it is more difficult to impregnate than the standard nylon fiber material. This can be detected by evaluating the impregnation properties according to Cobb's estimation. Although the Cobb value of standard wood pulp is usually greater than 2.8 g / g (according to DIN EN ISO 535, measured in accordance with a 78% NMMO aqueous solution at 75 ° C plus a 2-minute immersion time), the wood used in the present invention is preferably The pulp however showed a Cobb value of about 2.3 g / g. This requires adjustments during the preparation of the spinning solution, such as increased dissolution time (e.g. as explained in WO 94/28214 and WO 96/33934) and / or temperature adaptation and / or increased shear during dissolution (e.g. WO 96 / 33221, WO 98/05702 and WO 94/28217). This makes it possible to produce a spinning solution that allows the wood pulp described herein to be used in a standard fiber spinning process.
於本發明之一較佳形式中,用於製造萊纖產物,較佳為如本文所述之纖維,的木漿顯示於300至440 ml/g,特別是320至420 ml/g,更佳為320至400 ml/g的範圍中的掃描黏度(SCAN viscosity)。該掃描黏度係根據SCAN-CM 15:99使用銅乙二胺溶液(cupriethylenediamine solution)測定,該方法係專家已知的並且可藉著市售可得的裝置進行,例如可自PSL-Reotek購得的Auto PulpIVA PSLRheotek裝置。該掃描黏度係影響製造紡絲溶液期間的木漿加工之重要參數。即使是二木漿在組成等等方面顯示很高的一致性,但是不同的掃描黏度將導致加工期間完全不同的表現。於諸如該萊纖製程的直接溶解紡絲製程中,該木漿依原樣溶解於NMMO。與舉例來說膠絲製程(viscose process)相比,沒有熟成步驟,其中該纖維素的聚合度可順應該製程的需要進行調整。因此,對於該萊纖製程而言該原料木漿的黏度規格通常係於小目標範圍內。否則,可能會出現製造期間的問題。根據本發明,已發現該木漿黏度較佳為如上所述。較低的黏度會折損該萊纖產物的機械性質。特別是較高的黏度會導致該紡絲溶液的黏度提高,因此整個紡絲變得較慢。較慢的紡絲速度也導致較低的拉伸比(tensile ratio),那也會對該纖維結構及纖維性質產生顯著影響(Carbohydrate Polymers 2018, 181, 893-901)。這將需要程序調整而導致產能下降。一方面,使用具有此處界定的黏度的纖維素可實現高品質產物的簡單加工及製造。In a preferred form of the present invention, the wood pulp used to make the fiber product, preferably the fiber as described herein, is shown at 300 to 440 ml / g, especially 320 to 420 ml / g, more preferably SCAN viscosity in the range of 320 to 400 ml / g. The scanning viscosity is measured according to SCAN-CM 15:99 using a cupriethylenediamine solution. This method is known to experts and can be performed with commercially available devices, such as commercially available from PSL-Reotek Auto PulpIVA PSLRheotek device. This scanning viscosity is an important parameter that affects the processing of wood pulp during the manufacture of spinning solutions. Even though Erwood pulp shows high consistency in composition and so on, different scanning viscosities will lead to completely different performance during processing. In a direct dissolution spinning process such as the Lycra process, the wood pulp is dissolved in NMMO as it is. Compared with the viscose process, for example, there is no ripening step, in which the degree of polymerization of the cellulose can be adjusted according to the needs of the process. Therefore, the viscosity specification of the raw wood pulp is usually within a small target range for the fiber processing process. Otherwise, problems may occur during manufacturing. According to the present invention, it has been found that the viscosity of the wood pulp is preferably as described above. The lower viscosity can compromise the mechanical properties of the fiber product. In particular, higher viscosities lead to an increase in the viscosity of the spinning solution, and therefore the entire spinning becomes slower. Slower spinning speeds also result in lower tensile ratios, which can also have a significant impact on the fiber structure and fiber properties (Carbohydrate Polymers 2018, 181, 893-901). This will require program adjustments that will result in reduced capacity. On the one hand, the use of cellulose with a viscosity as defined herein enables simple processing and manufacturing of high-quality products.
如本文所用,該措辭"萊纖製程"或措辭"萊纖技術"及"萊纖程序"表示纖維素木漿或其他以纖維素為底質的原料於極性溶劑(例如N-甲基嗎啉N-氧化物(NMMO、NMO)或離子液體)中的直接溶解製程。在商業上,此技術用以製造一系列纖維素短纖維(在市場上可自Lenzing AG,Lenzing,Austria以註冊商標TENCEL®或TENCEL™購得),其廣泛用於紡織業或非織物業。其他由萊纖技術製得的纖維素成形體也已經有人製造出來。根據此製程,通常以所謂的乾濕紡絲製程使用成形機具擠出該纖維素溶液,並且獲得成形的溶液,例如在經過空氣間隙進入沉澱浴之後,在那裡藉由使該纖維素沉澱而獲得成形體。經過進一步的處理步驟之後,清洗模製品並且視需要地乾燥。用於製造萊纖纖維的製程係描述於例如US 4246221、WO 93/19230、WO 95/02082或WO 97/38153中。直到本發明討論與先前技藝相關的缺點並且討論本文所揭示並請求的新產物之獨特性質為止,特別是在使用實驗室裝備(尤其是於先前技藝中)的背景下或在(半工業)中試設備(pilot plant)及商業纖維紡紗單元的背景下,應將本發明理解為表示能就其生產能力界定如下的單元:
半工業中試設備:約1 kt/a
工業設備大於30 kt/aAs used herein, the terms "fabrication process" or "fabrication technology" and "fabrication process" refer to cellulose wood pulp or other cellulose-based raw materials in a polar solvent (such as N-methylmorpholine) N-oxide (NMMO, NMO) or ionic liquid). Commercially, this technology is used to make a series of cellulosic staple fibers (commercially available from Lenzing AG, Lenzing, Austria under the registered trademark TENCEL® or TENCEL ™), which are widely used in the textile or non-woven industry. Other cellulose shaped bodies made by Lycra technology have also been manufactured. According to this process, the cellulose solution is usually extruded using a molding machine in a so-called dry-wet spinning process and a shaped solution is obtained, for example, after entering the precipitation bath through an air gap, where it is obtained by precipitating the cellulose Shaped body. After going through further processing steps, the molded article is washed and dried if necessary. The process for making Lycra fibers is described, for example, in US 4246221, WO 93/19230, WO 95/02082 or WO 97/38153. Until the present invention discusses the disadvantages associated with prior art and discusses the unique properties of the new products disclosed and claimed herein, especially in the context of using laboratory equipment (especially in prior art) or in (semi-industrial) In the context of a pilot plant and a commercial fiber spinning unit, the present invention should be understood to mean a unit that can be defined in terms of its production capacity as follows:
Semi-industrial pilot plant: about 1 kt / a
Industrial equipment greater than 30 kt / a
在本發明的上下文中,據顯示,特別是以萊纖製程為背景的纖維製造時,將發生纖維製造和拉伸方向的取向。從紡絲原液(dope)中不同聚合物和其他組分的初始或多或少的無取向混合物,噴絲頭處的橫截面的強烈變窄導致該聚合物依製造方向的初始取向。經過該噴絲頭之後的氣隙中及於隨後的製程步驟期間的額外拉伸導致該聚合物的拉伸取向纖維結構。這些過程在專業文獻中是眾所周知的。In the context of the present invention, it has been shown that, particularly during the manufacture of fibers with a background of a lycra process, the orientation of the fiber manufacturing and drawing directions will occur. From the initial more or less non-oriented mixture of different polymers and other components in the spinning dope, the strong narrowing of the cross-section at the spinneret results in the initial orientation of the polymer in the manufacturing direction. Additional stretching in the air gap after passing through the spinneret and during subsequent processing steps results in a stretch-oriented fiber structure of the polymer. These processes are well known in the professional literature.
該纖維性質受該聚合物類型及組成的強烈影響。另外已知藉由該萊纖製程製造的纖維素纖維具有約44至47%的非常高的結晶度,而來自該膠絲製程的纖維具有約29至34%的結晶度。該結晶度描述該纖維素聚合物彼此相對的取向,因此,舉例來說,其吸收、溶脹及儲存水的能力。此外,該萊纖纖維的非結晶區中的聚合物鏈比該膠絲纖維中的聚合物鏈更有序。結果,與膠絲纖維相比,普通萊纖纖維膨脹較少並且不太適於高吸收性產品。The fiber properties are strongly influenced by the type and composition of the polymer. It is also known that cellulosic fibers made by the lycra process have a very high crystallinity of about 44 to 47%, and fibers from the rubber yarn process have a crystallinity of about 29 to 34%. The crystallinity describes the orientation of the cellulose polymers relative to each other, and thus, for example, their ability to absorb, swell, and store water. In addition, the polymer chains in the non-crystalline region of the spun fiber are more ordered than the polymer chains in the rayon fiber. As a result, ordinary lycra fibers swell less and are less suitable for high-absorbent products than rayon fibers.
根據本發明使用纖維素含量降低的纖維素意外地使得該聚合物的完全不同類型的聚集及因此該萊纖纖維的不同結構成為可能。其結晶度明顯較低,通常為40%或更低,例如39%或更低,舉例來說38%至30%,例如37%至33%。The use of cellulose with a reduced cellulose content according to the invention unexpectedly makes possible a completely different type of agglomeration of the polymer and thus a different structure of the fiber. Its crystallinity is significantly lower, typically 40% or lower, such as 39% or lower, for example 38% to 30%, such as 37% to 33%.
根據本發明的纖維的WRV值,與本文所述的其他較佳設計分離或組合,較佳為與本文所述纖維的結晶度值組合,較佳為70%或更高,特別是75%或更高,例如80%或更高,例如從70%到85%。The WRV value of the fiber according to the present invention is separated or combined with other preferred designs described herein, preferably in combination with the crystallinity value of the fiber described herein, preferably 70% or higher, especially 75% or Higher, such as 80% or higher, such as from 70% to 85%.
從文獻已知若該木聚醣的側鏈在製造過程中分離並且從純木聚醣溶液中沉澱出來,那麼木聚醣也會形成晶體結構(Fengel, Wegener p. 113; Fengel D, Wegener G (1989): Wood, Chemistry, Ultrastructure, Reactions; Walter de Gruyter Verlag)。這同樣適用於Mannan (同上;第119頁)。然而,於本發明中,可見到相反的效果。包括該纖維素的聚合物採混合物形式存於紡絲原液中,而且因此也紡出並沉澱。再者,該半纖維素仍然具有側基,因為該木聚醣的葡醣醛酸側基在酸消化條件之下相對穩定(Sixta H (Ed.) (2006): Handbook of Pulp Vol. 1; Wiley VCH p. 418)。該半纖維素因此滿足破壞該纖維素結晶化所需的所有條件,從而形成比標準萊纖纖維更無序的結構。因此,專家預期藉著更高的半纖維素含量及降低的纖維素含量,將導致無用的產品,特別是纖維。然而,頃出乎意料地顯示該半纖維素含量與該C5/C6比率組合可用以選擇性地控制產品性質。此不同糖聚合物的混合物仍然達成高於膠絲纖維的結晶度值,但是現在該纖維對水的整體可接近性增加,所以可使該保水能力(WRV) 顯著提高。此改進的吸收性對於各種應用是決定性的優點,例如,非織物。此降低結晶度與提昇萊纖纖維的保水能力之間的關係係如圖1所示,並且可如上所述般藉由降低纖維中的纖維素含量來調節。It is known from the literature that if the side chains of the xylan are separated during the manufacturing process and precipitated from the pure xylan solution, then xylan will also form a crystal structure (Fengel, Wegener p. 113; Fengel D, Wegener G (1989): Wood, Chemistry, Ultrastructure, Reactions; Walter de Gruyter Verlag). The same applies to Mannan (ibid .; p. 119). However, in the present invention, the opposite effect can be seen. The polymer including the cellulose is stored in the spinning dope as a mixture, and is therefore also spun out and precipitated. Furthermore, the hemicellulose still has side groups because the glucuronic acid side groups of the xylan are relatively stable under acid digestion conditions (Sixta H (Ed.) (2006): Handbook of Pulp Vol. 1; Wiley VCH p. 418). The hemicellulose therefore meets all the conditions required to disrupt the crystallization of the cellulose, thereby forming a more disordered structure than standard Lycra fibers. Therefore, experts expect that higher hemicellulose content and reduced cellulose content will result in useless products, especially fibers. However, it was unexpectedly shown that the hemicellulose content in combination with the C5 / C6 ratio can be used to selectively control product properties. This mixture of different sugar polymers still achieves a crystallinity value higher than that of the rayon fiber, but now the fiber's overall accessibility to water has increased, so the water retention capacity (WRV) can be significantly improved. This improved absorbency is a decisive advantage for various applications, such as non-wovens. The relationship between this reduction in crystallinity and the improvement of the water retention capacity of the fiber is shown in FIG. 1 and can be adjusted by reducing the cellulose content in the fiber as described above.
如實施例中所示,具有降低的纖維素含量的新萊纖纖維的品質與常規TENCEL®纖維相似。很明顯的是纖維強度略低於TENCEL®纖維,在實施例中測量為強度和工作能力(working capacity)。同時,該纖維素含量可能顯著降低,在實施例中記錄為葡聚醣值。藉由吸收其他木材組分,結晶度降低至多21%,並且吸收性顯著提昇至多27%,在實施例中測量為結晶度指數和保水能力。有趣的是,根據本發明的新萊纖纖維的結晶度介於常規TENCEL®纖維和非織物Lenzing Viscose®纖維之間;同時,該WRV係於Lenzing Viscose®的範圍中。該WRV因此比藉由該纖維的結晶度降低所能解釋的值更強烈地提昇。這是能藉著本發明實現的意外特性之清楚徵兆。其他組分例如特別是半纖維素,以及來自木材的木質素和附屬組分不僅提供產率的顯著提昇,即改進的可持續性,而且也提供產物性能的顯著改進,例如保水能力。
具體實例As shown in the examples, the quality of Sinlay fiber with reduced cellulose content is similar to conventional TENCEL® fiber. It is clear that the fiber strength is slightly lower than TENCEL® fiber, measured in the examples as strength and working capacity. At the same time, the cellulose content may be significantly reduced, which is reported as a glucan value in the examples. By absorbing other wood components, the crystallinity is reduced by up to 21%, and the absorbency is significantly increased by up to 27%, measured in the examples as the crystallinity index and water retention capacity. Interestingly, the crystallinity of the Sinclair fiber according to the present invention is between conventional TENCEL® fiber and non-woven Lenzing Viscose® fiber; meanwhile, the WRV is in the range of Lenzing Viscose®. The WRV is therefore increased more strongly than can be explained by a decrease in the crystallinity of the fiber. This is a clear sign of unexpected characteristics that can be achieved with the present invention. Other components such as, in particular, hemicellulose, and lignin and ancillary components from wood not only provide a significant increase in yield, that is, improved sustainability, but also a significant improvement in product performance, such as water retention capacity.
Concrete example
如申請專利範圍第1項所定義,根據本發明的木漿的特徵在於降低的纖維素含量、最小量的半纖維素及相對於該半纖維素的組成一定的C5/C6比率。As defined in item 1 of the scope of the patent application, the wood pulp according to the invention is characterized by a reduced cellulose content, a minimal amount of hemicellulose and a certain C5 / C6 ratio relative to the composition of the hemicellulose.
於較佳的形式中,該木漿,其也可為不同木漿的混合物(只要滿足基本條件),是具有7至50重量%,較佳為7至30重量%,更佳為15至25重量%,例如10至20重量%的半纖維素含量之木漿。In a preferred form, the wood pulp, which can also be a mixture of different wood pulps (as long as the basic conditions are met), has 7 to 50% by weight, preferably 7 to 30% by weight, and more preferably 15 to 25. % By weight, for example wood pulp with a hemicellulose content of 10 to 20% by weight.
根據本發明使用的木漿還較佳為含有至少9重量%木聚醣的木漿,更佳為至少10重量%木聚醣。只要滿足本發明中定義的比率,該甘露聚醣的比例可於寬廣的範圍內組合或獨立地選擇。合適的甘露聚醣含量位於0.1至10重量%的範圍中,例如0.1至9重量%,及0.1至6重量%,0.1至4重量%,5至10重量%,6至10重量%,0.1至9重量%等等。於實施形式中,該甘露聚醣含量係於0.1至1重量%的範圍中,較佳為與至少9重量%,較佳為至少10重量%的木聚醣含量組合。於其他設計中,錳含量較高,較佳為於6重量%或更高的範圍中。The wood pulp used according to the present invention is also preferably a wood pulp containing at least 9% by weight of xylan, more preferably at least 10% by weight of xylan. As long as the ratio defined in the present invention is satisfied, the ratio of the mannan can be combined or independently selected within a wide range. Suitable mannan content is in the range of 0.1 to 10% by weight, such as 0.1 to 9% by weight, and 0.1 to 6% by weight, 0.1 to 4% by weight, 5 to 10% by weight, 6 to 10% by weight, 0.1 to 9% by weight and so on. In an embodiment, the mannan content is in the range of 0.1 to 1% by weight, preferably in combination with at least 9% by weight, preferably at least 10% by weight of xylan content. In other designs, the manganese content is higher, preferably in the range of 6% by weight or more.
於較佳形式中,與上下文所述的形式分離或組合,該木漿中的纖維素含量係於小於等於90重量%至50重量%的範圍中,較佳為於90重量%至60重量%的範圍中,例如85重量%至70重量%。In a preferred form, separated from or combined with the form described above and below, the cellulose content of the wood pulp is in the range of 90% to 50% by weight, preferably 90% to 60% by weight. In the range of, for example, 85% to 70% by weight.
該纖維素與半纖維素的重量比率可介於1:1至20:1。該附屬組分的比例可為大於0.05重量%,較佳為大於0.2重量%,更佳為大於0.5重量%。出乎意料的是,據顯示藉著根據本發明的木漿中之此比例的附屬組分,可支持所製造的萊纖產物,特別是纖維,中的C5/C6比率是穩定的並且該半纖維素含量沒有顯著變化(即,與該木漿相比,該萊纖產物中的含量不會降低或僅降低到較小程度)。The weight ratio of the cellulose to the hemicellulose may be between 1: 1 and 20: 1. The proportion of the accessory component may be more than 0.05% by weight, preferably more than 0.2% by weight, and more preferably more than 0.5% by weight. Surprisingly, it has been shown that with this proportion of ancillary components in the wood pulp according to the present invention, the C5 / C6 ratio in the manufactured fiber products, especially fibers, is supported and the semi There was no significant change in the cellulose content (i.e. the content in the fiber product was not reduced or only reduced to a small extent compared to the wood pulp).
於另一較佳設計中,根據本發明的C5/C6比率達成如此高的保水能力,同時使以該萊纖產物的重量為基準計至多25重量%比例的金屬化合物,其通常以其氧化物及氫氧化物的形態存在(例如,為達阻燃目的之Mg(OH)2 或Al(OH)3 ),成為可能,這使得該纖維素比例進一步實質上降低。此金屬化合物特別是TiO2 、Al2O3 、MgO、SiO2 、CeO2 、Mg(OH)2 、Al(OH)3 、BN、ZnO,並且部分來自木材的礦物質組分或可加於該纖維素溶液中作為功能性添加物(阻燃劑、消光劑、殺菌劑...)。In another preferred design, the C5 / C6 ratio according to the present invention achieves such a high water retention capacity, while at the same time allowing a metal compound ratio of up to 25% by weight based on the weight of the fiber product, which is usually based on its oxide And the existence of hydroxide forms (for example, Mg (OH) 2 or Al (OH) 3 for flame retardant purposes), which makes it possible to further substantially reduce the cellulose ratio. This metal compound is especially TiO 2 , Al 2 O 3 , MgO, SiO 2 , CeO 2 , Mg (OH) 2 , Al (OH) 3 , BN, ZnO, and part of the mineral components from wood may be added to the fiber It is used as a functional additive (flame retardant, matting agent, bactericidal ...) in the vegetarian solution.
在另一較佳設計中,可製造出纖維素含量降至低於70%的萊纖纖維,這不僅滿足與已知萊纖纖維相比的實際要求(機械強度等),而且還由於本發明產生的新特性而更加適於某些應用。相關研究顯示所提出的組合物中之纖維特別顯示提昇的保水能力及於堆肥期間的快速生物降解性。In another preferred design, lycra fibers with a cellulose content of less than 70% can be manufactured, which not only meets the actual requirements (mechanical strength, etc.) compared to known lycra fibers, but also because of the invention The resulting new features are more suitable for certain applications. Relevant research has shown that the fibers in the proposed composition particularly show improved water retention and rapid biodegradability during composting.
根據本發明,據顯示非纖維素聚合物的C5/C6糖之比率為調節該纖維組成及其所得性質的重要因素。藉由調節此比率,再結合該半纖維素的含量,可調節所需的產物性質。According to the present invention, it has been shown that the C5 / C6 sugar ratio of the non-cellulosic polymer is an important factor in regulating the fiber composition and its resulting properties. By adjusting this ratio, combined with the hemicellulose content, the desired product properties can be adjusted.
在這種情況下,專家知道如何控制或調整該C5/C6比率。這可藉由混合各種木漿達成例如具有較高甘露聚醣含量的軟木漿與具有較高木聚醣含量的硬木漿。試驗證實調整設定的另一非常有效的方法。該C5與C6糖的比率可藉由設定特定蒸煮參數例如H因子來控制。這在圖2和3中有舉例說明。該H因子被認為是控制亞硫酸鹽蒸煮的必要參數(Sixta (Vol. 1 2006) 432頁)。其將蒸煮溫度及蒸煮時間彙總為一個規格。In this case, experts know how to control or adjust the C5 / C6 ratio. This can be achieved by mixing various wood pulps such as soft wood pulps with higher mannan content and hard wood pulps with higher xylan content. Tests have proven another very effective way to adjust settings. The C5 to C6 sugar ratio can be controlled by setting specific cooking parameters such as the H factor. This is illustrated in Figures 2 and 3. This H factor is considered to be a necessary parameter for controlling sulphite cooking (Sixta (Vol. 1 2006) p. 432). It summarizes the cooking temperature and cooking time into one specification.
圖2顯示使用山毛櫸作為實例的亞硫酸鹽沸騰時的H因子對硬木中半纖維素比率的影響。硬木中木聚醣的含量自然更高。隨著H因子的提高,使木聚醣降解得比甘露聚醣更多。該比率C5/C6降低了。Figure 2 shows the effect of H factor on the ratio of hemicellulose in hardwood when sulphite is boiled using beech as an example. The content of xylan in hardwood is naturally higher. With the increase of H factor, xylan was degraded more than mannan. The ratio C5 / C6 is reduced.
當使用軟木時,該半纖維素比率係另一方式。木材和木漿中的甘露聚醣比例較高。在這裡,與預期相反,如圖3所示,甘露聚醣分解的比木聚醣快。When using softwood, this hemicellulose ratio is another way. Higher proportions of mannan in wood and wood pulp. Here, contrary to expectations, as shown in Figure 3, mannan breaks down faster than xylan.
調節根據本發明的木漿組合物之另一方式是添加先前於其他製程或製程步驟中獲得的C5及/或C6糖,例如鹼萃取、冷鹼萃取或E步驟等。為了製造膠絲纖維,已知將溶解形式的半纖維素加於紡絲物料並且於其後進行聯合紡絲(joint spinning) (WO2014086883)。這樣便能製造具有降低的纖維素含量之膠絲纖維。這是唯一可能的,因為膠絲製程於水性介質中發生,並且該半纖維素相應地是鹼溶性的,所以纖維素黃原酸酯(cellulose xanthate)及已溶解的半纖維素可混合在一起並且一起紡絲。相反地,該木漿於該萊纖製程中溶解於NMMO或類似溶劑中,這意指不能添加鹼性或水溶液。其將會稀釋溶劑並且降低溶解度或甚至導致不希望的沉澱。因此,半纖維素不能在製造紡絲溶液時以溶液的形式添加,但是必須以不同的方式引進該製程。有一種可能是在該木漿製造過程時添加,所以該混合物可接著用該木漿來乾燥。Another way to adjust the wood pulp composition according to the present invention is to add C5 and / or C6 sugars previously obtained in other processes or process steps, such as alkali extraction, cold alkali extraction or E-step and the like. For the production of rayon fibers, it is known to add hemicellulose in a dissolved form to the spinning material and thereafter to perform joint spinning (WO2014086883). This makes it possible to produce viscose fibers having a reduced cellulose content. This is only possible because the process of gelatin yarns takes place in an aqueous medium and the hemicellulose is correspondingly alkali-soluble, so cellulose xanthate and dissolved hemicellulose can be mixed together And spin together. In contrast, the wood pulp is dissolved in NMMO or similar solvents during the process of the fiber, which means that no alkaline or aqueous solution can be added. It will dilute the solvent and reduce solubility or even cause unwanted precipitation. Therefore, hemicellulose cannot be added as a solution when manufacturing a spinning solution, but the process must be introduced in a different way. One possibility is to add during the wood pulp manufacturing process, so the mixture can then be dried with the wood pulp.
令人驚訝的是,頃發現密切關注該半纖維素組合物是萊纖模製品,特別是纖維,的技術製造之關鍵點。只有當C5部分的比例與C6部分的比例相關時,才能於該纖維結構中大規模使用半纖維素。該木聚醣與甘露聚醣的比率較佳為介於18:1至1:3之間,較佳為9:1至1:2。同時,此混合比率允許將0.5至5重量%的木質素(及/或其他附屬組分)加入該纖維結構中而不會損害所需的性質到不利的程度。Surprisingly, it has been found that paying close attention to the hemicellulose composition is a key point in the technical manufacturing of nylon fiber molded products, especially fibers. Only when the proportion of the C5 part is related to the proportion of the C6 part, can hemicellulose be used on a large scale in the fiber structure. The ratio of the xylan to the mannan is preferably between 18: 1 and 1: 3, and more preferably between 9: 1 and 1: 2. At the same time, this mixing ratio allows 0.5 to 5% by weight of lignin (and / or other accessory components) to be added to the fiber structure without compromising desired properties to an unfavorable degree.
本發明提供的纖維具有常見的纖維纖度,例如7 dtex或更低,舉例來說2,2 dtex或更低,例如1,3 dtex或更低,或甚至更低,例如0.9 dtex或更低,其取決於期望的應用。對於非織造領域的應用,典型的纖度為1.5至1.8 dtex,而例如1.2至1.5 dtex的較低纖度則適於紡織應用。本發明也包括具有更低纖度的纖維以及具有顯著更高纖度的纖維,例如10 dtex或更低,例如9 dtex或更低,或甚至7 dtex或更低。纖維纖度的合適下限於諸多形式下為0.5 dtex或更高的值,例如0.8 dtex或更高,及1,3 dtex或更高。此處揭露的上限和下限可加以組合,並且也包括結果產生的範圍,例如0.5至9 dtex。令人驚訝的是,不久的將來在這世上的發現將能製造出具有多種纖度的纖維,其能被用於整個纖維應用範圍,包括紡織品應用及非織物應用。The fibers provided by the present invention have common fiber deniers, such as 7 dtex or lower, for example 2, 2 dtex or lower, such as 1, 3 dtex or lower, or even lower, such as 0.9 dtex or lower, It depends on the desired application. For non-woven applications, typical deniers are 1.5 to 1.8 dtex, while lower deniers such as 1.2 to 1.5 dtex are suitable for textile applications. The invention also includes fibers having lower deniers as well as fibers having significantly higher deniers, such as 10 dtex or lower, such as 9 dtex or lower, or even 7 dtex or lower. The appropriateness of the fiber fineness is limited to values of 0.5 dtex or higher in many forms, such as 0.8 dtex or higher, and 1,3 dtex or higher. The upper and lower limits disclosed here can be combined and also include the range in which the results are produced, such as 0.5 to 9 dtex. Surprisingly, the discoveries made in this world in the near future will be able to produce fibers with multiple deniers, which can be used in the entire range of fiber applications, including textile and non-woven applications.
若本案引用了多個參數,則如此處所述般測定這些參數。基本上這些參數係藉著像這樣的纖維獲得的,包含最大量為1重量%的添加物,例如消光劑等等,並且該纖維不受製程的影響。然而,此處描述的纖維當然可含有正常用量的習用添加物,條件是這不會損害該紡絲溶液的製造及/或該纖維的製造過程。
以下實施例舉例說明本發明的多個態樣。
方法If multiple parameters are cited in this case, these parameters are determined as described herein. Basically, these parameters are obtained by fibers like this, and contain a maximum of 1% by weight of additives, such as matting agents, and the fiber is not affected by the process. However, the fibers described herein may of course contain normal amounts of conventional additives, provided that this does not harm the manufacturing of the spinning solution and / or the manufacturing process of the fiber.
The following examples illustrate various aspects of the invention.
method
結晶度指數[%]的測定
結晶度指數由拉曼光譜(Raman spectroscopy)來測定。此方法用來自X射線廣角方法(WAX)的數據來校準並且係由Röder等人公佈(2009) (Röder T、Moosbauer J、Kliba G、Schlader S、Zuckerstätter G及Sixta H (2009): Comparative Characterisation of Man-Made Regenerated Cellulose Fibers. Lenzing Reports,第87卷,98頁)。
保水能力的測定[%]
讓樣品於20 ±0.1 °C下溶脹過夜。經過進一步稀釋之後,根據Zellcheming Leaflet IV/33/57於3000倍重力加速下將樣品離心。該保水能力接著計算如下:
WRV = (濕樣品的重量- 乾樣品的重量)/乾樣品的重量 x 100
實施例Measurement of crystallinity index [%] The crystallinity index was measured by Raman spectroscopy. This method was calibrated with data from the X-ray wide-angle method (WAX) and published by Röder et al. (2009) (Röder T, Moosbauer J, Kliba G, Schlader S, Zuckerstätter G, and Sixta H (2009): Comparative Characterisation of Man-Made Regenerated Cellulose Fibers. Lenzing Reports, vol. 87, p. 98).
Determination of water retention capacity [%]
Allow the sample to swell overnight at 20 ± 0.1 ° C. After further dilution, the samples were centrifuged according to Zellcheming Leaflet IV / 33/57 under 3000 times gravity acceleration. This water retention capacity is then calculated as follows:
WRV = (weight of wet sample-weight of dry sample) / weight of dry sample x 100
Examples
木聚醣 - 甘露聚醣比率設定實施例
表1顯示使用變化亞硫酸氫鎂消化時的H因子之實施例,對二木材物種調整C5/C6比率的結果。
Example of setting xylan - mannan ratio <br/> Table 1 shows an example of adjusting the C5 / C6 ratio for two wood species using an example of the H factor when changing the magnesium bisulfite digestion.
桉樹燃料漿的實施例
在中試設備中,使用根據本發明的VisCBC製程由桉樹木材製造新的牛皮化學木漿。該H因子為1200,蒸煮液中的有效鹼度為25 g/l。經過TCF工序之後進行漂白。於表2中列出相關的製程資料及產物屬性。
於此新的具有降低的纖維素含量的化學木漿中,於該纖維成品中該木聚醣與甘露聚醣的比率已經被極度地提昇到121,而該纖維素含量已經保持得非常低約85%。此新型木漿完全滿足該萊纖製程用於製造新的具有降低的纖維素含量之萊纖纖維的需求。 Example of Eucalyptus Fuel Pulp <br/> In a pilot plant, a new cowhide chemical wood pulp was made from eucalyptus wood using the VisCBC process according to the present invention. The H factor is 1200 and the effective alkalinity in the cooking liquor is 25 g / l. After the TCF process, bleaching is performed. The relevant process data and product attributes are listed in Table 2.
In this new chemical wood pulp with reduced cellulose content, the ratio of the xylan to mannan in the fiber finished product has been extremely increased to 121, and the cellulose content has been kept very low at about 85%. This new wood pulp fully meets the needs of the Lycra fiber process for making new Lycra fibers with reduced cellulose content.
使用新的降低纖維素之木漿時纖維性質的實 施 例
表3彙總用於製造萊纖纖維的起始木漿之糖單體的含量。
表4顯示與用本發明的木漿製造的萊纖纖維所達成的性質相比,標準纖維(萊纖及膠絲纖維)的機械性質。結果令人印象深刻地證明本發明了的優點。
在中試設備試驗及根據本發明的萊纖纖維的大規模製造中,據顯示儘管纖維素含量相當低,但是就商業相關的纖度而言卻可達成可接受的強度及工作能力的值。 同時,該WRV急劇提昇,所以此纖維對於以前膠絲纖維所佔有的新應用領域變得有意義。然而,與市售的膠絲纖維相比,用本發明的萊纖纖維可達成顯著更高的機械性質。
因此,該新的本發明的萊纖纖維結合了先前商業上可獲得的萊纖及膠絲纖維的有利性質。
Table 3 summarizes the sugar monomer content of the starting wood pulp used to make the fiber.
Table 4 shows the mechanical properties of standard fibers (right fibers and rayon fibers) compared to the properties achieved by the right fibers made from the wood pulp of the present invention. The results impressively demonstrate the advantages of the invention.
In pilot plant tests and the large-scale manufacture of nylon fibers according to the present invention, it has been shown that despite the relatively low cellulose content, acceptable strength and workability values can be achieved in terms of commercially relevant fineness. At the same time, the WRV has risen sharply, so this fiber becomes meaningful for the new application areas previously occupied by rayon fibers. However, significantly higher mechanical properties can be achieved with the nylon fiber of the present invention than the commercially available rayon fiber.
Therefore, this new fiber of the present invention combines the advantageous properties of previously commercially available fiber and rayon fibers.
圖1顯示本發明的萊纖纖維及標準萊纖纖維之結晶度及保水能力(water retention capacity)的關聯性。FIG. 1 shows the correlation between the crystallinity and water retention capacity of the fiber and standard fiber of the present invention.
圖2顯示當使用山毛櫸木材時,將亞硫酸鹽木漿中木聚醣與甘露聚醣的比率當作H因子的函數。 Figure 2 shows the ratio of xylan to mannan in sulfite wood pulp as a function of the H factor when using beech wood.
圖3顯示當使用雲杉木材時,將亞硫酸鹽木漿中木聚醣與甘露聚醣的比率當作H因子的函數。 Figure 3 shows the ratio of xylan to mannan in sulphite wood pulp as a function of H factor when using spruce wood.
Claims (19)
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EP18160123.8A EP3536850A1 (en) | 2018-03-06 | 2018-03-06 | Pulp and lyocell articles with reduced cellulose content |
EP18160123.8 | 2018-03-06 |
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EP (2) | EP3536850A1 (en) |
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CA (1) | CA3092615C (en) |
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CN113109205A (en) * | 2021-03-29 | 2021-07-13 | 杭州融凯盛科技有限公司 | Method for rapidly detecting forming state of lyocell fibers |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4246221A (en) | 1979-03-02 | 1981-01-20 | Akzona Incorporated | Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent |
ATA53792A (en) | 1992-03-17 | 1995-02-15 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES, DEVICE FOR IMPLEMENTING THE METHOD AND USE OF A SPINNING DEVICE |
DE59306540D1 (en) | 1992-10-05 | 1997-06-26 | Hans Paluschinski | SLUDGE AND WASTEWATER SAMPLING DEVICE AND METHOD FOR SAMPLING |
US5456748A (en) | 1993-05-24 | 1995-10-10 | Courtaulds Fibres (Holdings) Ltd. | Premix storage hopper |
US5413631A (en) | 1993-05-24 | 1995-05-09 | Courtaulds (Holding) Limited | Formation of a cellulose-based premix |
AT401271B (en) | 1993-07-08 | 1996-07-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSE FIBERS |
GB9412501D0 (en) * | 1994-06-22 | 1994-08-10 | Courtaulds Fibres Holdings Ltd | Manufacture of fibre |
AT402410B (en) | 1995-04-19 | 1997-05-26 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING A CELLULOSE SUSPENSION |
AT409130B (en) | 1995-04-25 | 2002-05-27 | Chemiefaser Lenzing Ag | USE OF A DEVICE FOR HOLDING AND DELIVERING A HOMOGENEOUS CELLULOSE SUSPENSION |
GB9607456D0 (en) | 1996-04-10 | 1996-06-12 | Courtaulds Fibres Holdings Ltd | Spinning of filaments |
AT404594B (en) | 1996-08-01 | 1998-12-28 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING A CELLULOSE SUSPENSION |
US6306334B1 (en) | 1996-08-23 | 2001-10-23 | The Weyerhaeuser Company | Process for melt blowing continuous lyocell fibers |
US6331354B1 (en) | 1996-08-23 | 2001-12-18 | Weyerhaeuser Company | Alkaline pulp having low average degree of polymerization values and method of producing the same |
US6210801B1 (en) * | 1996-08-23 | 2001-04-03 | Weyerhaeuser Company | Lyocell fibers, and compositions for making same |
US6471727B2 (en) | 1996-08-23 | 2002-10-29 | Weyerhaeuser Company | Lyocell fibers, and compositions for making the same |
US6057438A (en) * | 1996-10-11 | 2000-05-02 | Eastman Chemical Company | Process for the co-production of dissolving-grade pulp and xylan |
US20020084045A1 (en) * | 1998-11-12 | 2002-07-04 | Dimitris Ioannis Collias | Compositions for improving physical strength properties and humidity resistance of paper products |
DE102004024029A1 (en) * | 2004-05-13 | 2005-12-08 | Zimmer Ag | Lyocell method and apparatus with metal ion content control |
DE102004024030A1 (en) * | 2004-05-13 | 2005-12-08 | Zimmer Ag | Lyocell process with polymerization-degree-dependent adjustment of the processing time |
US9845575B2 (en) * | 2009-05-14 | 2017-12-19 | International Paper Company | Fibrillated blend of lyocell low DP pulp |
AT514001B1 (en) | 2012-12-06 | 2016-03-15 | Chemiefaser Lenzing Ag | Process for the preparation of a cellulosic molding |
US20150184338A1 (en) * | 2013-12-31 | 2015-07-02 | Weyerhaeuser Nr Company | Treated kraft pulp compositions and methods of making the same |
US20160040360A1 (en) * | 2014-08-05 | 2016-02-11 | Celanese Acetate Llc | Processes for pretreating and purifying a cellulosic material |
US10239905B2 (en) * | 2017-01-30 | 2019-03-26 | The United States Of America As Represented By The Secretary Of Agriculture | Low temperature and efficient fractionation of lignocellulosic biomass using recyclable organic solid acids |
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CL2020002286A1 (en) | 2021-02-05 |
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EP3536850A1 (en) | 2019-09-11 |
ZA202006048B (en) | 2022-03-30 |
RU2020132856A (en) | 2022-04-06 |
CA3092615C (en) | 2022-11-29 |
CA3092615A1 (en) | 2019-09-12 |
RU2020132856A3 (en) | 2022-04-12 |
US20210002825A1 (en) | 2021-01-07 |
ES2968528T3 (en) | 2024-05-10 |
BR112020017780A2 (en) | 2020-12-22 |
FI3762537T3 (en) | 2024-01-17 |
CN111788348B (en) | 2023-03-28 |
CN111788348A (en) | 2020-10-16 |
TWI746936B (en) | 2021-11-21 |
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