TWI500838B - Tissue papers for household use - Google Patents
Tissue papers for household use Download PDFInfo
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- TWI500838B TWI500838B TW098110740A TW98110740A TWI500838B TW I500838 B TWI500838 B TW I500838B TW 098110740 A TW098110740 A TW 098110740A TW 98110740 A TW98110740 A TW 98110740A TW I500838 B TWI500838 B TW I500838B
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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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/002—Tissue paper; Absorbent paper
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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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Description
本發明係關於：衛生紙、化妝用面紙之類的面紙、紙巾等等的家庭用薄葉紙，更詳細地說，係關於：柔軟且手觸感良好，同時又具有優異的強度之家庭用薄葉紙。The present invention relates to household tissue paper for tissue paper, paper towels, and the like, such as toilet paper, cosmetic paper, and the like, and more particularly to household thin leaf paper which is soft and has good hand touch and excellent strength. .
以往，作為衛生紙、化妝用面紙之類的面紙、紙巾等等所謂的家庭用薄葉紙所使用的紙漿，例如係使用：從取自闊葉樹、針葉樹的木材碎片加以蒸解而得的化學紙漿所製造的泥漿狀態的軟泥狀紙漿(slushed pulp)、將這種軟泥狀紙漿脫水烘乾而得的乾紙漿(dry pulp)、或者將舊紙予以脫墨處理而得的脫墨舊紙紙漿等，將這些紙漿在尚未漂白的紙漿或已經漂白的紙漿的狀態下，或者在尚未打漿或已經打漿後的紙漿的狀態下，配合品質設計而予以單獨或混合地使用。In the past, the pulp used for household tissue paper, such as tissue paper, paper towel, and the like, is made of chemical pulp obtained by steaming wood chips obtained from broadleaf trees and conifers. Slushed pulp in the mud state, dry pulp obtained by dehydrating and drying the soft mud pulp, or deinked old paper pulp obtained by deinking the old paper, etc. These pulps are used singly or in combination with the quality design in the state of unbleached pulp or bleached pulp, or in the state of pulp which has not been beaten or has been beaten.
關於應如何地提昇面紙的重要品質指標的柔軟度、手觸感的技術，以往就已經被不斷地研究，已經有人提出各種方案，例如藉由適當地選擇：疊層抄紙的紙漿的種類、經調整其使用比例後的疊層面紙及其製造方法(專利文獻1、專利文獻2)、長網抄紙機、短網抄紙機、雙線抄紙機、圓網洋基抄紙機等的抄紙機，或者藉由將紙用柔軟劑例如：脂肪酸酯系柔軟化劑(專利文獻3)、第4級銨鹽型陽離子界面活性劑(專利文獻4)、胺基甲酸酯醇或其鹽、或者陽離子化物(專利文獻5)、非陽離子系界面活性劑(專利文獻6、專利文獻7)、聚磷酸鹽(專利文獻8)、聚矽氧烷(專利文獻9、專利文獻10)等的添加藥品加入軟泥狀紙漿內，以改善軟泥狀紙漿本身的滑順度，進而使手觸感變好且變柔軟的方法；此外，還有先將紙漿濃縮之後，藉由機械性的混合攪拌處理來使得纖維彎曲軟化(專利文獻11、專利文獻12)等等。The technique of how to improve the softness and hand touch of important quality indexes of facial tissue has been studied in the past, and various proposals have been made, for example, by appropriately selecting: the type of pulp to be laminated, A laminated paper having a ratio of use thereof and a method for producing the same (Patent Document 1 and Patent Document 2), a long-wire paper machine, a short-wire paper machine, a double-line paper machine, a rotary paper-type paper machine, or the like, or A softening agent for paper, for example, a fatty acid ester-based softening agent (Patent Document 3), a fourth-order ammonium salt-type cationic surfactant (Patent Document 4), a urethane or a salt thereof, or a cation Additives such as a compound (Patent Document 5), a non-cationic surfactant (Patent Document 6, Patent Document 7), a polyphosphate (Patent Document 8), and a polyoxane (Patent Document 9, Patent Document 10) In the soft muddy pulp, the method of improving the smoothness of the soft muddy pulp itself, thereby making the hand touch feeling good and soft; further, after the pulp is concentrated, the fiber is mechanically mixed and stirred to make the fiber Bending softening Patent Document 11, Patent Document 12) and the like.
前述使用添加藥品的方法，有時候雖然可以獲得良好的柔軟效果，但是因為起泡性較大，因此會有對於抄紙作業本身造成不便之虞慮，有時候則會有導致降低紙力與吸水性的問題。此外，藉由機械性的處理來使纖維彎曲的情況，則是必須多增加讓原料濃縮的工程，因此就能源的面而言較為不利，這些都是其問題點。The above-mentioned method of adding a drug sometimes has a good softening effect, but since the foaming property is large, there is a concern that the papermaking operation itself is inconvenient, and sometimes the paper strength and water absorption are lowered. The problem. Further, in the case where the fiber is bent by mechanical treatment, it is necessary to increase the amount of work for concentrating the raw material, and thus it is disadvantageous in terms of the energy source, and these are problems.
此外，為了提昇面紙的濕潤強度，主要係使用聚醯胺、聚胺、環氧樹脂等的濕潤紙力提昇劑，然而面紙本身會變得較剛直，就柔軟度、手觸感的方面而言，將會造成負面影響，這是其問題點。In addition, in order to enhance the wetting strength of the facial tissue, a moist paper strength enhancer such as polyamine, polyamine or epoxy resin is mainly used, but the facial tissue itself becomes relatively straight, in terms of softness and hand touch. In terms of it, it will have a negative impact, which is the problem.
此外，以往為了改善表面的平滑性，乃在面紙抄紙機之後，使用一組或兩組之由上下各一支的一對經充分研磨過的冷硬軋輥、金屬輥子所組成的壓光機。然而，利用這種壓光機為了要提昇平滑性因而提高線壓力的話，將會有導致厚度變薄，變得剛直而使手觸感也變硬的問題。In addition, in order to improve the smoothness of the surface, in the past, after a paper machine, one or two sets of calenders consisting of a pair of fully ground chill rolls and metal rolls are used. . However, with such a calender, in order to improve the smoothness and thereby increase the line pressure, there is a problem that the thickness becomes thin and becomes straight and the hand feel becomes hard.
[專利文獻1]日本特開昭54-46914號公報[Patent Document 1] Japanese Patent Laid-Open No. 54-46914
[專利文獻2]日本實開平4-66992號公報[Patent Document 2] Unexamined Japanese Patent Publication No. 4-66992
[專利文獻3]美國發明專利3,296,065號公報[Patent Document 3] U.S. Patent No. 3,296,065
[專利文獻4]日本特開昭48-22701號公報[Patent Document 4] Japanese Patent Laid-Open No. 48-22701
[專利文獻5]日本特開昭60-139897號公報[Patent Document 5] Japanese Laid-Open Patent Publication No. 60-139897
[專利文獻6]日本特開平2-99690號公報[Patent Document 6] Japanese Patent Laid-Open No. Hei 2-99690
[專利文獻7]日本特開平2-99691號公報[Patent Document 7] Japanese Patent Laid-Open No. 2-99691
[專利文獻8]日本特開平2-36288號公報[Patent Document 8] Japanese Patent Laid-Open No. 2-36288
[專利文獻9]日本特開平2-224626號公報[Patent Document 9] Japanese Patent Laid-Open No. Hei 2-224626
[專利文獻10]日本特開平3-900號公報[Patent Document 10] Japanese Patent Laid-Open No. 3-900
[專利文獻11]日本特開平5-23262號公報[Patent Document 11] Japanese Patent Laid-Open Publication No. 5-23262
[專利文獻12]日本特開平6-14848號公報[Patent Document 12] Japanese Patent Laid-Open No. Hei 6-14848
本發明的課題係在於提供：柔軟且手觸感良好，同時又具有優異的強度之家庭用薄葉紙。An object of the present invention is to provide a household thin leaf paper which is soft and has a good hand touch and has excellent strength.
本發明人等，經過不斷研究的結果，發現了：藉由含有將氣穴現象所生成的氣泡於破裂時所產生的衝撃力施予紙漿纖維而獲得的紙漿，能夠得到柔軟且手觸感良好，同時又具有優異的強度之家庭用薄葉紙之創見，進而完成了本發明。As a result of continuous research, the present inventors have found that a pulp obtained by applying a pulping force generated by breaking a bubble generated by a cavitation phenomenon to a pulp fiber can be soft and has a good touch. At the same time, the invention of the thin leaf paper for household use having excellent strength has completed the present invention.
根據本發明，係可獲得：柔軟且手觸感良好，同時又具有優異的強度之家庭用薄葉紙。According to the present invention, it is possible to obtain a household leaf paper which is soft and has a good hand touch and has excellent strength.
[用以實施本發明的最佳方式][Best way to implement the invention]
本發明的家庭用薄葉紙的特徵為：含有將氣穴現象所生成的氣泡於破裂時所產生的衝撃力施予紙漿纖維而獲得的紙漿。以下的說明中係將「將氣穴現象所生成的氣泡於破裂時所產生的衝撃力施予紙漿纖維」這件事情稱為「氣穴現象處理」。The household thin leaf paper of the present invention is characterized in that it contains pulp obtained by applying a punching force generated when a bubble generated by cavitation occurs at the time of cracking to a pulp fiber. In the following description, the "crushing force generated by the cavitation generated by the cavitation phenomenon is applied to the pulp fiber" is called "cavitation treatment".
作為本發明的氣穴現象處理的對象的紙漿並未特別地限定，係可使用：將木質纖維素材料利用鹼性蒸解藥液予以蒸解而得的化學紙漿(針葉樹的漂白牛皮紙紙漿(NBKP)或未漂白牛皮紙紙漿(NUKP)、闊葉樹的漂白牛皮紙紙漿(LBKP))、機械紙漿(磨碎木片紙漿(GP)、機械細磨紙漿(RGP)、熱機械處理紙漿(TMP)、化學熱機械處理紙漿(CTMP)等)、脫墨紙漿(DIP)等。化學紙漿則是可使用牛皮紙紙漿、聚硫紙漿、鈉鹼紙漿、鹼性亞硫酸鹽紙漿、碳酸鈉鹼紙漿、以及氧一鈉鹼紙漿等。The pulp which is the object of the cavitation treatment of the present invention is not particularly limited, and a chemical pulp (bleached kraft pulp (NBKP) of coniferous tree or a chemical pulp obtained by distilling a lignocellulosic material with an alkaline distilling solution may be used. Unbleached Kraft Pulp (NUKP), Hardwood Bleached Kraft Pulp (LBKP), Mechanical Pulp (Grated Wood Pulp (GP), Mechanical Fine Ground Pulp (RGP), Thermomechanical Treatment Pulp (TMP), Chemical Thermomechanical Treatment of Pulp (CTMP), etc., deinked pulp (DIP), and the like. For chemical pulp, kraft pulp, polysulfide pulp, sodium alkali pulp, alkaline sulfite pulp, sodium carbonate alkali pulp, and oxygen-sodium alkali pulp can be used.
前述化學紙漿亦可是：在前述的蒸解藥液中添加了作為蒸解助劑的環狀酮基化合物(例如：蒽醌、1,4-二羥-9,10-二酮蒽等)之後才進行蒸解的紙漿。又，作為前述化學紙漿，特別適用在本發明中的是牛皮紙紙漿，這種牛皮紙紙漿亦可為：利用蒸解液的分割添加以及在連續蒸解爐内部的並流蒸解與向流蒸解所組成的「修正鹼性蒸解法」所製得的紙漿。這些化學紙漿，亦可適當將：未漂白紙漿的狀態、漂白紙漿的狀態，或者未打漿的狀態、打漿紙漿的狀態，予以單獨使用或者混合使用。The chemical pulp may be obtained by adding a cyclic ketone compound (for example, hydrazine, 1,4-dihydroxy-9,10-dione oxime, etc.) as a digestion aid to the above-mentioned distillate solution. Digested pulp. Further, as the chemical pulp, particularly suitable for use in the present invention is kraft pulp, which may be composed of a divided addition of a distillate and a co-current digestion and a steaming in a continuous distillation furnace. Correct the pulp obtained by the alkaline distillation method. These chemical pulps may be used singly or in combination with the state of the unbleached pulp, the state of the bleached pulp, or the state of the unpulped pulp, and the state of the pulping pulp.
關於氣穴現象處理，更詳細說明的話，係將因氣穴現象所生成的氣泡於破裂時所產生的衝撃力施加到紙漿纖維，促使紙漿的外部原纖維化(外部起毛)，並且又抑制内部原纖維化以調整濾水度。作為氣穴現象處理，係可採用：WO 2005/012632號公報所述的氣穴現象噴流處理。Regarding the treatment of the cavitation phenomenon, in more detail, the flushing force generated by the bubble generated by the cavitation phenomenon is applied to the pulp fiber to promote the external fibrillation of the pulp (external fuzzing), and the internal reaction is suppressed. Fibrillation to adjust the degree of filtration. As the cavitation treatment, the cavitation jet treatment described in WO 2005/012632 can be employed.
此外，亦可將氣穴現象處理與機械式的打漿處理組合在一起來將紙漿纖維予以外部原纖維化。在紙漿懸濁液中，除了紙漿纖維以外，即使含有：舊紙或含在紙塊內的填料或含在印刷顏料中的無機物微粒子也無妨。氣穴現象處理除了可以促進紙漿纖維的外部原纖維化之外，又可抑制内部原纖維化，因此與傳統方法之使用打細機等的裝置利用機械力量來進行打漿處理後的紙漿比較的話，在相同的濾水度的條件下，可獲得更為膨鬆且具有優異的強度的紙漿。因此含有利用這種氣穴現象處理所獲得的外部原纖維的紙漿之家庭用薄葉紙，係更柔軟而且具有優異的強度。In addition, the cavitation treatment can be combined with the mechanical beating treatment to externally fibrillate the pulp fibers. In the pulp suspension, it is possible to contain, in addition to the pulp fibers, old paper or a filler contained in the paper block or inorganic fine particles contained in the printing pigment. In addition to promoting the external fibrillation of the pulp fibers, the cavitation treatment can suppress the internal fibrillation. Therefore, if the apparatus using a fine machine such as a conventional machine uses mechanical strength to compare the pulp after the beating treatment, Under the same degree of filtration, a pulp which is more bulky and has excellent strength can be obtained. Therefore, the household tissue paper containing the pulp which is treated by the cavitation treatment of the external fibrils is softer and has excellent strength.
藉由氣穴現象處理所調製後的紙漿的加拿大標準濾水度，在化學紙漿的情況下，以50～650ml的範圍為宜，在機械紙漿或舊紙(脫墨)紙漿的情況下，以50～400ml的範圍為宜。此外，在混合了前述兩種紙漿的情況下，總合的加拿大標準濾水度係以100～550ml的範圍為宜。The Canadian standard water filtration degree of the prepared pulp by the cavitation treatment is preferably in the range of 50 to 650 ml in the case of chemical pulp, and in the case of mechanical pulp or old paper (deinked) pulp. A range of 50 to 400 ml is preferred. Further, in the case where the above two kinds of pulps are mixed, the total Canadian standard water filtration degree is preferably in the range of 100 to 550 ml.
其次，將詳細說明氣穴現象處理。所謂「氣穴現象」係如加藤先生的著作(加藤洋治編著：新版氣穴現象基礎與最近的進歩；槙書店，1999年出版)所記載，當氣穴現象氣泡的破裂時，對於數μm程度的局部區域將會產生高達數GPa程度的衝撃力量，而且以微觀方式來觀察的話，當氣泡破裂時，會因為隔熱壓縮而讓溫度上昇到達數千℃。其結果，在發生了氣穴現象的情況下，溫度將會一起上昇。基於這些現象，氣穴現象對於流體機械也會帶來例如：損傷、振動、降低性能等等的不利因素的一面，因此以往都將技術課題放在：有必要將其控制成不發生氣穴現象。近年來針對於氣穴現象的研究急速地進展，已經發展到可將氣穴現象噴流的流體力學上的參數當作操作因子，高精度地控制氣穴現象的發生區域、甚至於可以控制衝撃力的大小。其結果，藉由控制氣泡的破裂衝撃力，可令人期待有效地活用這種強力的能量。因此，可藉由執行依據流體力學上的參數的操作和調整，而可高精度地控制氣穴現象。已經顯示出可以保持技術上的作用效果的穩定性，因而已經不再是以往的那種在流體機械中自然發生的伴隨著無法控制的不良影響的氣穴現象，而是將經過控制後的氣穴現象所生成的氣泡積極地導入到紙漿懸濁液中，有效利用其能量的做法就是本發明的特徵。Next, the cavitation treatment will be described in detail. The so-called "cavitation phenomenon" is such as the work of Mr. Kato (edited by Kato Yoji: the basis of the new version of cavitation and the recent entry; the bookstore, published in 1999), when the cavitation bubble bursts, for a few μm The local area will produce a punching force of up to a few GPa levels, and when viewed in a microscopic manner, when the bubble bursts, the temperature rises to several thousand °C due to the thermal compression. As a result, in the case where cavitation occurs, the temperature will rise together. Based on these phenomena, the cavitation phenomenon also brings about adverse factors such as damage, vibration, and performance degradation of the fluid machine. Therefore, in the past, the technical subject has been placed: it is necessary to control it to not cause cavitation. . In recent years, research on cavitation has progressed rapidly, and it has been developed to use the hydrodynamic parameters of the cavitation jet as an operational factor, to control the occurrence of cavitation with high precision, and even to control the flushing force. the size of. As a result, by controlling the rupture force of the bubble, it is expected that the powerful energy can be effectively utilized. Therefore, the cavitation phenomenon can be controlled with high precision by performing the operation and adjustment according to the parameters of the hydrodynamics. It has been shown to maintain the stability of the technical effect, and thus is no longer the cavitation phenomenon that occurs naturally in fluid machines with uncontrollable adverse effects, but the controlled gas. The bubble generated by the hole phenomenon is actively introduced into the pulp suspension, and the use of the energy efficiently is a feature of the present invention.
本發明中之作為氣穴現象的生成手段，雖然可以例舉出：利用液體噴流的方法、使用超音波震盪子的方法、使用超音波震盪子與號角狀的增幅放大器的方法、利用雷射照射的方法等，但是並不限定為這些方法。使用液體噴流的方法，因為氣穴現象氣泡的生成效率高，可形成具有更強力的破裂衝撃力的氣穴現象氣泡雲，對於紙漿纖維的作用效果很大，所以較為合宜。根據前述方法所發生的氣穴現象係與以往的流體機械中自然發生的伴隨著無法控制的不良影響的氣穴現象明顯地不同。In the present invention, as a means for generating a cavitation phenomenon, a method using a liquid jet, a method using an ultrasonic oscillator, a method using an ultrasonic oscillator and a horn-shaped amplifier, and a laser irradiation can be exemplified. The method, etc., but is not limited to these methods. The liquid jet method is used because the cavitation bubble generation efficiency is high, and a cavitation bubble cloud having a stronger rupture force can be formed, which is more effective for the pulp fiber. The cavitation phenomenon which occurs according to the above method is significantly different from the cavitation phenomenon which naturally occurs in the conventional fluid machine and which has an uncontrollable adverse effect.
如上所述，作為氣穴現象處理，係適合採用WO2005/012632號公報所述的這種利用液體噴流的氣穴現象噴流處理，以下將詳細地說明。As described above, as the cavitation treatment, it is suitable to use the cavitation jet process using the liquid jet as described in WO2005/012632, which will be described in detail below.
所謂「液體噴流」係指：液體或者液體之中散佈著或混合著固體粒子、氣體的流體的噴流，也就是指：紙漿或無機物粒子的泥漿或含氣泡的液體噴流。此處所稱的氣體亦可包含因氣穴現象所生成的氣泡。The term "liquid jet" refers to a jet of a fluid in which a solid particle or a gas is dispersed or mixed in a liquid or a liquid, that is, a slurry of pulp or inorganic particles or a jet of liquid containing bubbles. The gas referred to herein may also contain bubbles generated by cavitation.
氣穴現象係當液體受到加速，局部地方的壓力變成較之該液體的蒸氣壓更低的時候才會發生，因此流速以及壓力特別的重要。基於這種理由，用來表達氣穴現象狀態的基本上的無次元數、氣穴現象數(Cavitation Number)σ係被定義成如下所列的數式(請參考加藤洋治編著的「新版氣穴現象基礎與最近的進歩」，槙書店於1999年出版)。The cavitation phenomenon occurs when the liquid is accelerated and the local pressure becomes lower than the vapor pressure of the liquid, so the flow rate and pressure are particularly important. For this reason, the basic non-dimensional number, Cavity Number σ system used to express the cavitation state is defined as the following formula (please refer to the new version of the cavitation edited by Kato Yoji) The basis of the phenomenon and the recent advancement, published by the bookstore in 1999).
(p∞ ：一般流的壓力(絕對壓力)、U∞ ：一般流的流速、pv ：流體的蒸氣壓(絕對壓力)、ρ：密度)(p ∞ : general flow pressure (absolute pressure), U ∞ : general flow velocity, p v : fluid vapor pressure (absolute pressure), ρ: density)
此處，所謂「氣穴現象數很大」係表示該流體流經的地方處於難以發生氣穴現象的狀態。特別是氣穴現象噴流的這種經由噴嘴或者限流孔管來發生氣穴現象的情況下，可從噴嘴上游側壓力p1 (絕對壓力)、噴嘴下游側壓力p2 (絕對壓力)、試料水的飽和蒸氣壓pv (絕對壓力)，將氣穴現象數σ改寫成下列數式(2)，在氣穴現象噴流中，因為p1 、p2 、pv 間的壓力差很大，係p1 遠大於p2 遠大於pv 的狀態，因此可將氣穴現象數σ更進一步以下列的數式來近似(請參考H.Soyama,J. Soc. Mat. Sci. Japan,47(4),381 1998)。Here, the term "the number of cavitation phenomena is large" means that the place where the fluid flows is in a state where cavitation is less likely to occur. In particular, in the case where cavitation occurs via a nozzle or a restriction orifice in the cavitation jet, the pressure p 1 (absolute pressure) from the upstream side of the nozzle, the pressure p 2 (absolute pressure) on the downstream side of the nozzle, and the sample can be obtained. The saturated vapor pressure p v (absolute pressure) of water rewrites the cavitation phenomenon σ into the following formula (2). In the cavitation jet, because the pressure difference between p 1 , p 2 , and p v is large, The line p 1 is much larger than the state where p 2 is much larger than p v , so the cavitation phenomenon σ can be further approximated by the following equation (refer to H. Soyama, J. Soc. Mat. Sci. Japan, 47 ( 4), 381 1998).
是以，氣穴現象數σ係可藉由：噴嘴的上游側壓力與下游側壓力的兩個數值來予以表現。此外，在本發明的實施例中所量測的壓力，全部都是儀器計測壓，本發明中的氣穴現象數σ可依下列數式(3)來表示。Therefore, the number of cavitation phenomena σ can be expressed by two values of the upstream side pressure and the downstream side pressure of the nozzle. Further, the pressures measured in the embodiments of the present invention are all measured by the instrument, and the number of cavitation phenomena σ in the present invention can be expressed by the following formula (3).
[數式3][Expression 3]
σ=p4/p3σ=p4/p3
(惟，p3：噴嘴上游側壓力(儀器計測壓)、p4：噴嘴下游側壓力(儀器計測壓))(However, p3: pressure on the upstream side of the nozzle (instrument measurement pressure), p4: pressure on the downstream side of the nozzle (instrument measurement pressure))
本發明中的氣穴現象的條件，係以上述氣穴現象數σ為0.001以上0.5以下為宜，0.003以上0.2以下更佳，0.01以上0.1以下特佳。當氣穴現象數σ未達0.001的情況下，氣穴現象氣泡於破裂時之與周圍的壓力差很低，所以效果變小，較之0.5更大的情況下，水流的壓力差很低，氣穴現象很難發生。The condition of the cavitation phenomenon in the present invention is preferably 0.001 or more and 0.5 or less, and more preferably 0.003 or more and 0.2 or less, and more preferably 0.01 or more and 0.1 or less. When the number of cavitation phenomena σ is less than 0.001, the pressure difference between the cavitation bubble and the surrounding is very low, so the effect becomes smaller, and the pressure difference of the water flow is lower than that of 0.5. Cavitation is hard to happen.
又，當經由噴嘴或者限流孔管將噴射液予以噴射出去以使其發生氣穴現象的時候，噴射液的壓力(噴嘴上游側壓力)係以0.01MPa(儀器計測壓)以上60MPa(儀器計測壓)以下為宜，0.7MPa(儀器計測壓)以上30MPa(儀器計測壓)以下更佳；2MPa(儀器計測壓)以上15MPa(儀器計測壓)以下特佳。如果噴嘴上游側壓力未達0.01MPa(儀器計測壓)的話，與噴嘴下游側壓力之間難以產生壓力差因而作用效果很小。又，如果噴嘴上游側壓力較之60MPa(儀器計測壓)更高的情況下，必須使用到特殊的泵浦及壓力容器，所消耗的能源變大，因此在於成本上較為不利，而且會使得紙漿纖維受到過度的損傷，不適合作為製紙原料來使用。另外，容器内的壓力(噴嘴下游側壓力)係以静壓為0.05MPa(儀器計測壓)以上2.6MPa(儀器計測壓)以下為宜。對於下游側也施加壓力的做法，乃是藉由對於收容被噴射液(紙漿懸濁液)的容器加壓，使得氣穴現象氣泡破裂區域的壓力變高，氣泡與周圍的壓力差變大，所以氣泡可更急激烈地破裂，使得衝撃力變得更大。此外，容器内的壓力如果變得過高的話，氣穴現象本身就變得不易發生。因此容器内的壓力與噴射液的壓力之間的壓力比((儀器計測壓)/(儀器計測壓))係在0.001～0.5的範圍為宜。Further, when the ejection liquid is ejected through the nozzle or the restriction tube to cause cavitation, the pressure of the ejection liquid (pressure on the upstream side of the nozzle) is 0.01 MPa (measured by the instrument) and 60 MPa (instrument measurement) The pressure is preferably below, 0.7 MPa (measured by the instrument) or more than 30 MPa (measured by the instrument); 2 MPa (measured by the instrument) is preferably 15 MPa or more. If the pressure on the upstream side of the nozzle is less than 0.01 MPa (measured by the instrument), a pressure difference is unlikely to occur between the pressure on the downstream side of the nozzle and the effect is small. In addition, if the pressure on the upstream side of the nozzle is higher than 60 MPa (measured by the instrument), a special pump and pressure vessel must be used, and the energy consumed is increased, so that the cost is disadvantageous and the pulp is made. The fiber is excessively damaged and is not suitable for use as a papermaking material. In addition, the pressure in the container (pressure on the downstream side of the nozzle) is preferably hereinafter referred to as a static pressure of 0.05 MPa (measured by instrument) or 2.6 MPa (measured by instrument). The pressure is also applied to the downstream side by pressurizing the container for accommodating the sprayed liquid (pulp suspension), so that the pressure in the rupture zone of the cavitation bubble becomes high, and the pressure difference between the bubble and the surrounding becomes large. Therefore, the bubbles can be more violently broken, making the punching force larger. In addition, if the pressure inside the container becomes too high, the cavitation phenomenon itself becomes less likely to occur. Therefore, the pressure ratio ((instrument measurement pressure) / (instrument measurement pressure)) between the pressure in the container and the pressure of the ejection liquid is preferably in the range of 0.001 to 0.5.
又，噴射液的噴流的速度係以1m/秒以上200m/秒以下的範圍為宜，20m/秒以上100m/秒以下的範圍更佳。如果噴流的速度未達1m/秒的情況下，壓力的降低很少，氣穴現象很難發生，所以其效果很弱。另一方面，如果噴流的速度較之200m/秒更大的情況下，需要高壓，因此必須使用特別的裝置，在成本上較為不利。Further, the speed of the jet flow of the ejection liquid is preferably in the range of 1 m/sec to 200 m/sec, and more preferably in the range of 20 m/sec to 100 m/sec. If the velocity of the jet is less than 1 m/sec, the pressure drop is small, and cavitation is difficult to occur, so the effect is weak. On the other hand, if the speed of the jet flow is larger than 200 m/sec, a high pressure is required, so that a special device must be used, which is disadvantageous in terms of cost.
本發明中的氣穴現象處理雖然可以選擇在水槽等的任意的容器内或者在配管内，但並不限定於這些。此外，雖然也可採用單次處理(one-pass)的方式來進行處理，但是藉由使其循環好幾次的做法，可更為增大效果。此外，可以使用複數個氣穴現象產生手段，以並列方式或者串列方式進行處理。The cavitation treatment in the present invention can be selected in any container such as a water tank or in a pipe, but is not limited thereto. In addition, although it is also possible to perform processing in a one-pass manner, it is possible to increase the effect by circulating it several times. In addition, a plurality of cavitation generation means can be used to perform processing in a side by side manner or in a tandem manner.
用來使之產生氣穴現象的噴流，雖然也可以在製紙漿機的這種開放在大氣中的容器中來產生噴流，但是為了要控制氣穴現象，最好是在壓力容器中來產生噴流。The jet used to cause cavitation, although it is also possible to produce a jet in the open-air container of the pulper, in order to control the cavitation, it is preferable to generate a jet in the pressure vessel. .
在本發明中，例如：在利用液體噴流來產生氣穴現象的方法，係對於紙漿懸濁液，例如：將蒸餾水、自來水、工業用水、製紙工程中回收的再利用水、紙漿搾水、還流水、紙漿懸濁液、酒精等，當作噴射液體進行噴射，但是並不限定於這些。最好是將紙漿懸濁液本身當作噴射液體來加以噴射，除了發生在噴流周圍的氣穴現象所產生的作用效果之外，又可獲得從限流孔高壓噴射時的流體力學上的剪力，因此可發揮更大的作用效果。此外，使用紙漿懸濁液作為噴射液體的情況下，亦可將作為處理對象的所有紙漿量都予以循環來進行處理。In the present invention, for example, a method of generating cavitation by a liquid jet is for a pulp suspension, for example, distilled water, tap water, industrial water, reuse water recovered in a papermaking process, water-squeezed pulp, and The running water, the pulp suspension, the alcohol, and the like are sprayed as the ejection liquid, but are not limited thereto. It is preferable to spray the pulp suspension itself as a spray liquid. In addition to the effect of the cavitation phenomenon occurring around the jet, the hydrodynamic shear of the high pressure jet from the restriction orifice can be obtained. Force, so it can play a greater role. Further, when a pulp suspension is used as the ejection liquid, all the amount of pulp to be treated may be circulated and processed.
利用液體噴流來產生氣穴現象以進行處理的情況下，基於氣泡發生效率的觀點而言，處理對象亦即紙漿懸濁液的固形分濃度係以5重量%以下為宜，3重量%以下更佳，0.1～1.5重量%的範圍最佳。When the cavitation phenomenon is generated by the liquid jet to perform the treatment, the solid content concentration of the pulp suspension to be treated is preferably 5% by weight or less, and 3% by weight or less, from the viewpoint of bubble generation efficiency. Preferably, the range of 0.1 to 1.5% by weight is optimal.
此外，處理時的紙漿懸濁液的pH值，係以pH1～13為宜，pH3～12更佳，pH4～11特佳。如果pH未達1的話，裝置的腐蝕等將會成為問題，基於材質及保養等的觀點，較為不利。另一方面，如果pH超過13的話，將會讓紙漿纖維發生變黃現象，因而降低白色度，所以並不適宜。保持在鹼性條件這一邊的做法對於紙漿纖維的膨潤性較良好，因為可增加OH活性游離基的生成量，所以較為合宜。Further, the pH of the pulp suspension at the time of the treatment is preferably pH 1 to 13, pH 3 to 12 is more preferred, and pH 4 to 11 is particularly preferred. If the pH is less than 1, the corrosion of the device or the like will become a problem, and it is disadvantageous based on the viewpoints of materials and maintenance. On the other hand, if the pH exceeds 13, the pulp fiber will be yellowed, thereby lowering the whiteness, so it is not suitable. The method of maintaining the alkaline condition is excellent in the swelling property of the pulp fiber, and it is preferable because the amount of formation of the OH active radical can be increased.
本發明是藉由提高液體的噴射壓力，以增大噴射液的流速，因而產生更強力的氣穴現象。再者，藉由對於收容被噴射液的容器加壓，使得氣穴現象的氣泡破裂的區域的壓力變高，因為氣泡與周圍的壓力差變大，所以氣泡將會激烈地破裂而使得衝撃力也變大。此處所稱的「噴射液」係指：以高壓狀態從限流孔噴射出來的液體，「被噴射液」係指：被噴射到容器内或配管内的液體。氣穴現象係受液體中的氣體的量所影響，當氣體過多的情況下，將會引起氣泡與氣泡彼此的衝突以及合而為一，因此破裂衝撃力量將會被其他的氣泡所吸收，產生緩衝效果，導致衝撃力變弱。因此，因為受到了溶存氣體與蒸氣壓的影響，所以其處理溫度必須在融點以上沸點以下。液體若是以水作為媒質的情況下，處理溫度選定在0～80℃的範圍為宜，更好是選定在10℃～60℃的範圍的話，能夠獲得很高的效果。一般都認為處理溫度選定在融點與沸點之間的中間點，衝撃力會趨於最大，因此在水溶液的情況下，係以50℃前後最為適合，但是，即使在50℃以下的溫度，也不會受到蒸氣壓的影響，因此只要是在前述的範圍的話，就可獲得很高的效果。如果是較之80℃更高的溫度的話，用來產生氣穴現象的壓力容器的耐壓性會明顯的降低，容器很容易損壞，所以並不適宜。The present invention increases the injection pressure of the liquid to increase the flow rate of the spray liquid, thereby producing a more powerful cavitation phenomenon. Further, by pressurizing the container for accommodating the liquid to be ejected, the pressure in the region where the cavitation bubble is broken becomes high, and since the pressure difference between the bubble and the surrounding becomes large, the bubble is violently broken and the squeezing force is also Become bigger. The term "jetting liquid" as used herein refers to a liquid that is ejected from a restriction orifice in a high pressure state, and "injected liquid" refers to a liquid that is ejected into a container or in a pipe. The cavitation phenomenon is affected by the amount of gas in the liquid. When the gas is too much, it will cause the bubbles and the bubbles to collide with each other and merge into one. Therefore, the rupture force will be absorbed by other bubbles, resulting in The cushioning effect causes the punching force to weaken. Therefore, since it is affected by the dissolved gas and the vapor pressure, the treatment temperature must be below the boiling point above the melting point. When the liquid is water as a medium, the treatment temperature is preferably in the range of 0 to 80 ° C, and more preferably in the range of 10 ° C to 60 ° C, and a high effect can be obtained. It is generally considered that the treatment temperature is selected at the intermediate point between the melting point and the boiling point, and the punching force tends to be the largest. Therefore, in the case of an aqueous solution, it is most suitable before and after 50 ° C, but even at a temperature below 50 ° C, Since it is not affected by the vapor pressure, a high effect can be obtained as long as it is within the above range. If the temperature is higher than 80 ° C, the pressure resistance of the pressure vessel used to generate cavitation will be significantly lowered, and the container is easily damaged, so it is not suitable.
在本發明中，藉由添加界面活性劑之類的可降低液體的表面張力的物質的話，可以降低產生氣穴現象時所需的能量。所添加的物質係可以為公知或新型的界面活性劑，係可舉出例如：脂肪酸鹽、高級烷基硫酸鹽、烷基苯璜酸酸鹽、高級酒精、烷基酚、脂肪酸之類的環氧烷附加物等的非離子界面活性劑、陰離子界面活性劑、陽離子界面活性劑、兩性界面活性劑、或者有機溶劑等，但是並不限定於這些界面活性劑。亦可為由這些界面活性劑的單一成分所組成的，或者兩種以上的成分的混合物。至於添加量，只要是能夠降低噴射液及/或被噴射液的表面張力所需的量即可。此外，至於添加的場所，只要是在較之產生氣穴現象的場所更前面的工序中的任何一處場所即可，但如果是將液體予以循環處理的情況下，則即使是在產生氣穴現象的場所以後的地方才進行添加亦無妨。In the present invention, by adding a substance such as a surfactant which lowers the surface tension of the liquid, the energy required to generate cavitation can be reduced. The substance to be added may be a known or novel surfactant, and examples thereof include a fatty acid salt, a higher alkyl sulfate, an alkyl benzoate, a higher alcohol, an alkyl phenol, a fatty acid or the like. A nonionic surfactant such as an oxyalkylene additive, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or an organic solvent is not limited to these surfactants. It may also be composed of a single component of these surfactants or a mixture of two or more components. The amount of addition may be any amount required to reduce the surface tension of the ejection liquid and/or the liquid to be sprayed. In addition, as for the place to be added, it may be any one of the processes ahead of the place where cavitation occurs, but if the liquid is to be recycled, even if cavitation is generated It is no problem to add the place after the phenomenon.
在本發明中，相對於全紙漿分之實施氣穴現象處理後的紙漿的配合率(含量)雖然並無特別的限定，但是配合率愈高的話，愈可獲得強度更高且柔軟的家庭用薄葉紙。基於這種觀點，相對於全紙漿的絕對乾燥重量，實施氣穴現象處理後的紙漿的配合率(含量)係以5重量%以上為宜，30～100重量%更佳，60～100重量%特佳。如果配合率未達5重量%的話，看不出來在柔軟度、手觸感上有所改變，無法提昇強度。In the present invention, the blending ratio (content) of the pulp after the cavitation treatment with respect to the whole pulp is not particularly limited, but the higher the blending ratio, the higher the strength and the softness of the household. Thin leaf paper. From this point of view, the blending ratio (content) of the pulp after the cavitation treatment is preferably 5% by weight or more, more preferably 30 to 100% by weight, and 60 to 100% by weight, based on the absolute dry weight of the whole pulp. Very good. If the blending ratio is less than 5% by weight, the softness and hand touch are not changed, and the strength cannot be increased.
家庭用薄葉紙雖然係由單一層或複數層所構成的，但是，可將單一層或複數層以氣穴現象處理紙漿單獨地進行抄紙，亦可混合兩種以上的氣穴現象處理紙漿來進行抄紙，此外，亦可在氣穴現象處理後的紙漿中混合了傳統的軟泥狀紙漿、乾紙漿、脫墨紙漿(DIP)之後才進行抄紙。Although the household leaf tissue is composed of a single layer or a plurality of layers, the single layer or the plurality of layers may be separately subjected to papermaking by cavitation treatment, or may be mixed with two or more cavitation processes for papermaking. In addition, papermaking can also be carried out after mixing the conventional soft muddy pulp, dry pulp, and deinked pulp (DIP) in the pulp after the cavitation treatment.
將由複數層所組成的家庭用薄葉紙兩張重疊在一起進行疊層的情況下，如果係將含有氣穴現象處理紙漿的層置於外側來予以重疊的話，因為手所觸摸到的層就是該含有氣穴現象處理紙漿的這一層，所以可更進一步提昇手觸感。又，將含有氣穴現象處理紙漿的這一層壓接到洋基烘乾機上進行烘乾，而將這個面配置在兩張重疊而成的家庭用薄葉紙的外側的話，將可更進一步提昇手觸感。In the case where two sheets of household leaf paper composed of a plurality of layers are stacked and laminated, if the layer containing the cavitation-treated pulp is placed on the outside to be overlapped, since the layer touched by the hand is the content The cavitation process treats this layer of pulp, so it can further enhance the feel of the hand. Moreover, the lamination containing the cavitation-treated pulp is attached to the Yanji dryer for drying, and the face is disposed on the outer side of the two overlapping household thin-leaf papers, which further enhances the hand touch. sense.
又，作為氣穴現象處理紙漿以外的紙漿，係可以將例如：化學紙漿(針葉樹的漂白牛皮紙紙漿(NBKP)或未漂白牛皮紙紙漿(NUKP)、闊葉樹的漂白牛皮紙紙漿(LBKP))或未漂白牛皮紙紙漿(LUKP)等)、機械紙漿(磨碎木片紙漿(GP)、機械細磨紙漿(RGP)、熱機械處理紙漿(TMP)、化學熱機械處理紙漿(CTMP)等)、脫墨紙漿(DIP)之類的紙漿，以任意的比例來混合使用。Further, as a cavitation treatment pulp other than pulp, for example, chemical pulp (bleached kraft pulp (NBKP) or unbleached kraft pulp (NUKP), hardwood bleached kraft pulp (LBKP)) or unbleached kraft paper can be used. Pulp (LUKP), etc., mechanical pulp (grinded wood pulp (GP), mechanical finely ground pulp (RGP), thermomechanical treated pulp (TMP), chemical thermomechanical treated pulp (CTMP), etc.), deinked pulp (DIP) The pulp is mixed and used in any ratio.
經過氣穴現象處理後的紙漿，雖然是受到促進其外部原纖維化後的紙漿，但是在有些情況下，亦可獲得具有鱗片狀的外部原纖維的紙漿，以下將針對這些進行說明。Although the pulp which has been subjected to cavitation treatment is subjected to pulp which promotes external fibrillation, in some cases, pulp having scaly outer fibrils can be obtained, which will be described below.
根據磯貝先生的著作(磯貝明著「纖維素的材料化學」；東京大學出版會，p68，2001年出版)，所謂「紙漿的打漿」，係指：對於含水狀態的紙漿纖維施予機械性的擦刷應力，在紙漿纖維内部的微原纖維之間製造出空隙(内部原纖維化)，讓紙漿纖維的外側的原纖維起毛(外部原纖維化)，使其比表面積增大，以資提昇紙漿纖維對於水的膨潤性，同時會產生將纖維予以局部性地切斷，以及纖維的外周面剝離後的微細纖維。According to the work of Mr. Isobe (Isobe Ming, "Material Chemistry of Cellulose"; University of Tokyo Press, p68, 2001), "Pulping of pulp" means mechanically imparting pulp fibers in a hydrated state. The brushing stress creates voids (internal fibrillation) between the microfibrils inside the pulp fibers, causing the fibrils on the outer side of the pulp fibers to fluff (external fibrillation), and the specific surface area thereof is increased to increase The pulp fiber has a swellability to water, and at the same time, microfibers are obtained by partially cutting the fibers and peeling off the outer peripheral surface of the fibers.
藉由紙漿的打漿處理，在造紙時所形成的纖維間的結合面積將會增加，各種力學物性、光學物性、液體吸收性將會改變。然而，若將紙漿纖維以分子大小的基準來觀察的話，在打漿處理的過程中，纖維素的分子量僅有少許的降低，結晶化度幾乎未改變。這是被認為：因為非晶性之具有親水性的半纖維素部分係有如緩衝軟墊般地可以吸收機械能量的緣故。By the pulping treatment of the pulp, the bonding area between the fibers formed during papermaking will increase, and various mechanical properties, optical properties, and liquid absorbability will change. However, if the pulp fibers are observed on the basis of the molecular size, the molecular weight of the cellulose is only slightly lowered during the beating treatment, and the degree of crystallization is hardly changed. This is considered to be because the amorphous hemicellulose fraction is capable of absorbing mechanical energy like a cushioned cushion.
此外，根據島地先生等的著作(島地謙等人共著「木材的組織」；森北出版社，p55，1976年出版)，從以一般方法進行打漿後的木材紙漿所觀察到的外部原纖維，係指：以光學顯微鏡所觀察到的幅寬0.4～1μm程度的絲狀的構造物，所謂「微原纖維」係指：存在於細胞壁中的要素性的構造單位，係具有9～37nm程度的幅寬的纖維素分子的集合體。在本發明所使用的具有鱗片狀的形態的外部原纖維之紙漿中，所稱的「具有特徵性的鱗片狀的形態的外部原纖維」，係指：幅寬3μm以上，較佳為具有與紙漿纖維的幅寬同等程度為止的大小之纖維表面的剝離或起毛，前述的微原纖維在横向相連而形成集合體，變成幅寬較大的層者，也就是，纖維壁表面的微原纖維保持在層構造的狀態下產生剝離者。此外，厚度是從9nm起訖2μm的範圍也是其特徵。此外，在利用電子顯微鏡觀察纖維的時候，最好是在阻止氫結合的乾燥狀態下來進行測定，這是因為如果只是單純地將纖維烘乾的情況下，會因為毛細管現象導致外部原纖維被吸附到纖維表面，難以判別之故，很難很精準地觀察到這種原纖維。In addition, according to the work of Mr. Shijiji, etc. (the organization of wood by the island, etc.; Mori Press, p55, 1976), the external fibrils observed from the wood pulp after beating in a general method. It is a filamentous structure having a width of 0.4 to 1 μm observed by an optical microscope. The term "microfibril" refers to a structural unit of the element that exists in the cell wall and has a degree of 9 to 37 nm. A collection of wide-width cellulose molecules. In the pulp of the outer fibrils having a scaly form used in the present invention, the term "external fibrils having a characteristic scaly form" means a width of 3 μm or more, preferably with The surface of the pulp fiber is peeled or fluffed to the same extent as the width of the fiber, and the microfibrils are connected in the transverse direction to form an aggregate, which becomes a layer having a large width, that is, a microfibril on the surface of the fiber wall. The peeler is produced while maintaining the layer structure. Further, the range in which the thickness is from 2 nm to 2 μm is also characteristic. In addition, when observing the fiber by an electron microscope, it is preferable to carry out the measurement in a dry state in which hydrogen bonding is prevented, because if the fiber is simply dried, the external fibril is adsorbed due to capillary action. It is difficult to discriminate into the surface of the fiber, and it is difficult to observe the fibril very accurately.
本發明中的鱗片狀的外部原纖維的特徵是：被分子量為一萬以上的高分子量的染料所染色。亦即，外部原纖維係指：可吸附分子量為一萬以上的高分子量的染料之微原纖維集合體。至於分子量為一萬以上的染料，雖然係可舉出例如：Simon氏等人的文献(F.L. Simons,Tappi,33(7),312(1950))、以及Xiaochun氏等人的文献(Y. Xiaochun et al.,Tappi Journal,78(6),175(1995).)中所記載的這種Direct Orange 15(old Color Index(CI)no,621、或者含有CI Constitution no. 40002/3)的CI Constitution no.40000～40006等的柑橘染料，但是只要是可將以纖維素為主體的纖維予以染色的物質的話即可，並無特別的限定。The scaly outer fibrils in the present invention are characterized by being dyed with a high molecular weight dye having a molecular weight of 10,000 or more. That is, the outer fibril means a microfibril aggregate which can adsorb a high molecular weight dye having a molecular weight of 10,000 or more. As for the dye having a molecular weight of 10,000 or more, for example, the literature of Simon et al. (FL Simons, Tappi, 33(7), 312 (1950)), and the literature of Xiaochun et al. (Y. Xiaochun) Et al., CI of Direct Orange 15 (old Color Index (CI) no, 621, or CI Constitution no. 40002/3) as described in Tappi Journal, 78(6), 175 (1995). The citrus dyes such as Constitution No. 40000 to 40006 are not particularly limited as long as they are those which can dye fibers mainly composed of cellulose.
前述分子量為一萬以上的染料，根據Xiaochun氏等的文献的記載的話，利用光散亂測定可知其為流體力學上的大小為5nm以上的分子，無法滲透進入到紙漿纖維表面所存在的未達5nm的細孔。另一方面，由紙漿纖維表面的微原纖維的集合體所構成的原纖維，係露出在紙漿纖維的外側，因此，前述分子量為一萬以上的染料分子很容易接近，所以可藉由吸附而能夠選擇性地將原纖維部分予以染色。The dye having a molecular weight of 10,000 or more is described by the literature of Xiaochun et al., and it is known that the molecule having a hydrodynamic size of 5 nm or more cannot be infiltrated into the surface of the pulp fiber by light scattering measurement. 5nm pores. On the other hand, the fibrils composed of the aggregate of microfibrils on the surface of the pulp fibers are exposed on the outer side of the pulp fibers. Therefore, the dye molecules having a molecular weight of 10,000 or more are easily accessible, so that they can be adsorbed. The fibril portion can be selectively dyed.
為了要以光學方式特別針對原纖維部分來加以觀察，係以前述文献所記載的方式，使用Direct Blue 1(old Color Index(CI)no.518、或者CI Constitution no.24410)或Direct Blue 4、Direct Blue 15、Direct Blue 22、Direct Blue 151之類的低分子染料，將纖維全體予以染色，即可加強其對比度而可更容易觀察。雖然在纖維全體上都吸附著低分子的染料，但是因為高分子的染料的吸附力更強，因此可將低分子的染料予以置換。其結果，可吸附高分子染料(柑橘染料)的原纖維部分係被染成橘色，無法吸附高分子染料的纖維細孔部分則可被低分子染料(藍色染料)所染色，因此得以將原纖維部分特別強調出來。至於低分子的染料，係含有：分子量未達10000，較好是分子量未達2000，更好是分子量300～1500的分子51%以上的染料。In order to observe optically specifically for the fibril portion, Direct Blue 1 (old Color Index (CI) no. 518, or CI Constitution no. 24410) or Direct Blue 4 is used in the manner described in the aforementioned documents. Low-molecular dyes such as Direct Blue 15, Direct Blue 22, and Direct Blue 151 dye the entire fiber to enhance contrast and make it easier to observe. Although a low molecular dye is adsorbed on the entire fiber, the dye of the polymer is more strongly adsorbed, so that the low molecular dye can be replaced. As a result, the fibril portion of the adsorbable polymer dye (citrus dye) is dyed orange, and the pore portion of the fiber which cannot adsorb the polymer dye can be dyed by the low molecular dye (blue dye), so that it can be The fibril portion is especially highlighted. The low molecular dye contains a dye having a molecular weight of less than 10,000, preferably a molecular weight of less than 2,000, more preferably 51% or more of a molecular weight of 300 to 1,500.
本發明之具有鱗片狀的外部原纖維的紙漿，其纖維以一根為單位來考量時，以下列數式4來表示的外部原纖維部分的面積率為20%以上，並且以下列數式5來表示的外部原纖維部分的周圍長率為1.5以上為宜。本發明的紙漿的鱗片狀的外部原纖維與一般的原纖維比較時，表面積較大，因此這些數值也變大。In the pulp having the scaly outer fibrils of the present invention, when the fibers are measured in units of one, the area ratio of the outer fibril portion expressed by the following formula 4 is 20% or more, and the following formula 5 The peripheral length of the outer fibril portion shown is preferably 1.5 or more. When the scaly outer fibrils of the pulp of the present invention are compared with ordinary fibrils, the surface area is large, and therefore these values are also increased.
外部原纖維部分的面積率(%)=[(外部原纖維部分的面積)/(外部原纖維部分的面積+紙漿纖維的全表面積)]×100 (數式4)Area ratio (%) of the outer fibril portion = [(area of outer fibril portion) / (area of outer fibril portion + total surface area of pulp fiber)] × 100 (Expression 4)
外部原纖維部分的周圍長率=(外部原纖維部分的周圍長+紙漿纖維的全周圍長)/(紙漿纖維的全周圍長) (數式5)The peripheral length of the outer fibril portion = (the circumference of the outer fibril portion + the total circumference of the pulp fiber) / (the total circumference of the pulp fiber) (Expression 5)
[作用][effect]
含有經氣穴現象處理後的紙漿的面紙的手觸感與強度都變成優異的理由，被認為是有下列的原因。The reason why the touch feeling and the strength of the facial tissue containing the pulp treated by the cavitation phenomenon are excellent is considered to be the following reason.
一般而言，在高蓬鬆度(密度低)且表面平滑的情況下，可以提昇面紙的手觸感。然而，如上所述，經氣穴現象處理後的紙漿，是將外部原纖維化予以特別加強促進的紙漿。亦即，如WO2006/085598公報所記載般地，因為是既能夠保住纖維的剛直性，又能夠促進外部原纖維化，所以與利用雙碟式磨碎機之類的傳統的機械方式處理比較的話，如果是將紙漿調配成：蓬鬆度為同等程度的情況下，紙張強度係有所提昇，如果是將紙漿調配成：同等強度的話，則紙張的蓬鬆度變得更高。In general, in the case of high loft (low density) and a smooth surface, the hand touch of the tissue can be improved. However, as described above, the pulp treated by the cavitation phenomenon is a pulp which is particularly enhanced by external fibrillation. In other words, as described in WO2006/085598, since it is capable of retaining the rigidity of the fiber and promoting the external fibrillation, it is compared with the conventional mechanical treatment such as a two-disc grinder. If the pulp is formulated to have the same degree of bulkiness, the paper strength is improved. If the pulp is blended to the same strength, the bulkiness of the paper becomes higher.
又，如果係使用經氣穴現象處理後的紙漿的話，可很容易將金屬輥子等的平滑面轉印到紙面上，因此紙張也很容易變成平滑。Further, if the pulp treated by the cavitation phenomenon is used, the smooth surface of the metal roller or the like can be easily transferred to the paper surface, so that the paper is easily smoothed.
基於這些理由，含有經氣穴現象處理後的紙漿的面紙被認為是手觸感與強度都有變優異的傾向。For these reasons, the facial tissue containing the pulp treated by cavitation is considered to have excellent hand touch and strength.
[實施例][Examples]
以下將舉出實施例及比較例來具體地說明本發明，但是本發明並不限定為這種實施例。此外，在實施例、比較例中所示的%，如果未特別地說明的話，係指：重量%。將下列的實施例及比較例中所調製的紙漿利用雙線型三層式的洋基抄紙機來進行抄紙。皺紋則是藉由採取：烘乾機與捲紙盤之間的速度差的方式，讓紙張產生乾皺紋。如果並未特別聲明的話，係將這個面紙原紙之與洋基烘乾機接觸的面(YD面)朝向外側(與使用者的手接觸這一側)的方式，兩張重疊在一起，將這個面朝外側地兩張疊層在一起之後，接觸到洋基烘乾機，然後將已經烘乾後的面，利用軟壓光機予以壓光。紙漿，無論是實施例或是比較例的情況下，都是採用：將日本國内產的闊葉樹碎木片以牛皮紙紙漿法來進行製造，且經過漂白後的漢特白色度(brightness by Hunter)為84%的闊葉樹漂白紙漿。Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to such Examples. Further, % shown in the examples and comparative examples means: % by weight unless otherwise specified. The pulp prepared in the following Examples and Comparative Examples was subjected to papermaking using a two-line three-layer Yankee paper machine. Wrinkles are caused by dry wrinkles by taking the difference in speed between the dryer and the reel. If it is not specifically stated, the two sides of the face paper (YD face) that is in contact with the Yankee dryer are facing outward (in contact with the user's hand), and the two are overlapped. After the two sheets facing each other are laminated together, they are exposed to the Yankee dryer, and then the dried surface is calendered by a soft calender. The pulp, whether in the case of the examples or the comparative examples, is produced by using a domestically produced broad-leaved tree chip in a kraft pulp process, and the bleached hector whiteness (brightness by Hunter) is 84% of broadleaf tree bleached pulp.
又，在實施例以及比較例中所使用的評判方法如下。Further, the evaluation methods used in the examples and comparative examples are as follows.
＜手觸感＞<Hand touch>
委託10名評審員，進行手觸感、及肌膚觸感的評判。以下列的區別方式來加以表示。Ten judges were commissioned to judge the touch of the hand and the feeling of the skin. It is expressed in the following different ways.
非常好：◎，好：○，普通：△，不佳：×Very good: ◎, good: ○, ordinary: △, poor: ×
＜拉伸強度(縱向)的測定法＞<Measurement of tensile strength (longitudinal)>
拉伸強度：在MD方向、CD方向上，將試料裁剪成15mm寬度，各方向的拉伸強度係以單一層(1 ply)來進行測定，利用下列數式計算出來的數值就當做是拉伸強度。Tensile strength: The sample was cut into a width of 15 mm in the MD direction and the CD direction, and the tensile strength in each direction was measured in a single layer (1 ply), and the value calculated by the following formula was regarded as stretching. strength.
拉伸強度(g)=(MD拉伸強度×CD拉伸強度)1/2 Tensile strength (g) = (MD tensile strength × CD tensile strength) 1/2
＜蓬鬆度的測定法＞<Measurement of Bulkness>
將試料以10層重疊在一起時的紙張厚度(mm)當作蓬鬆度。The paper thickness (mm) when the samples were overlapped by 10 layers was taken as the bulkiness.
＜單位面積重量的測定＞<Measurement of unit area weight>
依據日本工業規格JIS P 8124：1998(ISO 536：1995)來進行測定。The measurement was carried out in accordance with Japanese Industrial Standard JIS P 8124:1998 (ISO 536:1995).
＜氣穴現象處理紙漿的調整＞<Adjustment of Pulp Treatment Pulp>
氣穴現象處理係利用第1圖所示的氣穴現象噴流式處理裝置來進行的。第1圖中，試料槽1内收容著未圖示的紙漿懸濁液(濃度1.1%)，試料槽1內***溫度感應器12與攪拌器13。試料槽1的紙漿懸濁液係利用中介著閥柱泵4的預定的配管，被當作噴射液來導入到氣穴現象噴流容器3。在氣穴現象噴流容器3的下部設有噴嘴2，更詳細地說，試料槽1的紙漿懸濁液是從噴嘴2被噴射到噴流容器3内。此外，在從試料槽1的側部朝向噴流容器3的配管上設置有供水閥9、循環閥10，將試料槽1内的紙漿懸濁液當成被噴射液供給到噴流容器3内。在從試料槽1的側部朝向噴嘴2的另一個配管上則是介裝著一個上游側壓力控制閥5。另外，在從噴流容器3的上部朝向試料槽1的另一個配管上則是介裝著一個下游側壓力控制閥6，藉由調整各個壓力控制閥5、6，即可調整送到噴嘴2的紙漿懸濁液的噴射壓。又，在噴嘴2的輸入側係設有一個上游側壓力計7，在噴流容器3的上部係設有一個下游側壓力計8。此外，在噴流容器3的下部係設有一個排水閥11。The cavitation treatment is performed using the cavitation jet flow processing apparatus shown in Fig. 1. In the first drawing, a pulp suspension (concentration: 1.1%) (not shown) is accommodated in the sample tank 1, and the temperature sensor 12 and the agitator 13 are inserted into the sample tank 1. The pulp suspension of the sample tank 1 is introduced into the cavitation flow nozzle 3 as a spray liquid by a predetermined pipe through which the spool pump 4 is interposed. The nozzle 2 is provided in the lower portion of the cavitation jet container 3, and more specifically, the pulp suspension of the sample tank 1 is ejected from the nozzle 2 into the jet container 3. Further, a water supply valve 9 and a circulation valve 10 are provided in a pipe from the side of the sample tank 1 toward the jet flow container 3, and the pulp suspension in the sample tank 1 is supplied as the liquid to be sprayed into the jet flow container 3. On the other pipe from the side of the sample tank 1 toward the nozzle 2, an upstream side pressure control valve 5 is interposed. Further, on the other pipe from the upper portion of the jet flow container 3 toward the sample tank 1, a downstream side pressure control valve 6 is interposed, and by adjusting the respective pressure control valves 5, 6, the feed to the nozzle 2 can be adjusted. The spray pressure of the pulp suspension. Further, one upstream side pressure gauge 7 is provided on the input side of the nozzle 2, and one downstream side pressure gauge 8 is provided on the upper side of the jet flow container 3. Further, a drain valve 11 is provided in the lower portion of the jet container 3.
[實施例1][Example 1]
在三層之中的上層及下層的原料，係以下列方式調製。將闊葉樹漂白牛皮紙紙漿的紙漿薄片在低濃度製紙漿機中進行解離，調整到想要的濃度後，使用第1圖所示的氣穴現象噴流式處理裝置(噴嘴口徑1.5mm)，將噴射液的壓力(噴嘴上游側壓力)設定在8MPa(儀器計測壓，噴流的流速80m/秒)，將被噴射容器内的壓力(噴嘴下游側壓力)設定在0.4MPa(儀器計測壓)，進行單次(one pass)處理。此外，使用濃度為3重量%的紙漿懸濁液當作噴射液，對於容器内的紙漿懸濁液(濃度為3重量%)實施氣穴現象處理，將加拿大標準濾水度設定為435ml，製造出原料A。從原料A以及中層原料B(係將闊葉樹漂白牛皮紙紙漿的紙漿薄片在低濃度製紙漿機進行解離，加拿大標準濾水度設定為500ml者)來製造面紙。將抄紙出來的面紙的單位面積重量調節為16.6g/m2 。The raw materials of the upper layer and the lower layer among the three layers are prepared in the following manner. The pulp sheet of the hardwood bleached kraft pulp is dissociated in a low-concentration pulping machine, and after adjusting to a desired concentration, the cavitation jet processing device (nozzle diameter: 1.5 mm) shown in Fig. 1 is used to spray the liquid. The pressure (pressure on the upstream side of the nozzle) is set at 8 MPa (measurement pressure of the instrument, flow rate of the jet flow is 80 m/sec), and the pressure in the injection container (pressure on the downstream side of the nozzle) is set at 0.4 MPa (measured by the instrument), and is performed once. (one pass) processing. Further, a pulp suspension having a concentration of 3% by weight was used as a spray liquid, and a pulp suspension (concentration: 3% by weight) in the container was subjected to cavitation treatment, and the Canadian standard water filtration degree was set to 435 ml. Raw material A. The tissue paper was produced from the raw material A and the intermediate raw material B (the pulp sheet of the hardwood bleached kraft pulp was dissociated in a low-concentration pulping machine, and the Canadian standard water filtration degree was set to 500 ml). The basis weight of the paper which was taken out of paper was adjusted to 16.6 g/m 2 .
[比較例1][Comparative Example 1]
對於上層及下層的原料，以雙碟式磨碎機進行打漿處理來取代實施氣穴現象處理，將加拿大標準濾水度設定為470ml，製造出原料C。從原料C以及中層原料B來製造出面紙。將抄紙出來的面紙的單位面積重量調節為16.6g/m2 。For the raw materials of the upper layer and the lower layer, a double-disc grinder was used for the beating treatment instead of the cavitation treatment, and the Canadian standard water filtration degree was set to 470 ml to produce the raw material C. A facial tissue is produced from the raw material C and the intermediate raw material B. The basis weight of the paper which was taken out of paper was adjusted to 16.6 g/m 2 .
如表1所示，實施例1與比較例1進行比較時，手觸感雖然是同等程度，但是實施例1較之比較例1的拉伸強度提高約20%。實施例1較之比較例1的強度也大幅地提昇，而蓬鬆度才稍微降低一點。As shown in Table 1, when the first embodiment was compared with the comparative example 1, the hand touch was the same, but the tensile strength of the first example was improved by about 20% as compared with the comparative example 1. The strength of Example 1 was also greatly improved compared to Comparative Example 1, and the bulkiness was slightly lowered.
[實施例2][Embodiment 2]
對於上層及下層的原料施予與實施例1相同的處理，將加拿大標準濾水度設定為420ml，製造出原料D。在原料D以及中層原料B中添加入濕潤紙力增強劑0.1%(相對於絕對乾燥紙漿重量)來製造面紙。將抄紙出來的面紙的單位面積重量調節為13.0g/m2 。The raw materials of the upper layer and the lower layer were treated in the same manner as in Example 1, and the standard water filtration degree of Canada was set to 420 ml to prepare a raw material D. To the raw material D and the intermediate raw material B, 0.1% of the wet paper strength enhancer (relative to the absolute dry pulp weight) was added to produce a facial tissue. The basis weight of the paper which was taken out of paper was adjusted to 13.0 g/m 2 .
[比較例2][Comparative Example 2]
對於上層及下層的原料施予與比較例1相同的處理，將加拿大標準濾水度設定為410ml，製造出原料E。在原料E以及中層原料B中添加入濕潤紙力增強劑0.1%(相對於絕對乾燥紙漿重量)來製造面紙。將抄紙出來的面紙的單位面積重量調節為13.0g/m2 。The raw materials of the upper layer and the lower layer were treated in the same manner as in Comparative Example 1, and the Canadian standard water filtration degree was set to 410 ml to produce a raw material E. To the raw material E and the intermediate raw material B, 0.1% of the wet paper strength enhancer (relative to the absolute dry pulp weight) was added to produce a facial tissue. The basis weight of the paper which was taken out of paper was adjusted to 13.0 g/m 2 .
如表2所示，實施例2係較之比較例2的手觸感更良好，拉伸強度則近乎同等程度。此外，實施例2係較之比較例2的蓬鬆度提昇約7%。As shown in Table 2, Example 2 showed better hand touch feeling than Comparative Example 2, and the tensile strength was almost the same. Further, Example 2 was improved by about 7% as compared with Comparative Example 2.
[實施例3][Example 3]
對於上層及下層的原料，使用氣穴現象噴流式處理裝置(噴嘴口徑1.5mm)，將噴射液的壓力(噴嘴上游側壓力)設定為8MPa(儀器計測壓，、噴流的流速80m/秒)，將被噴射容器内的壓力(噴嘴下游側壓力)設定為0.4MPa(儀器計測壓)，進行兩次(two pass)處理，除此之外，其餘都是進行與實施例1相同的處理，將加拿大標準濾水度設定為390ml，來製造出原料F。在原料F以及中層原料B中添加入濕潤紙力增強劑0.1%(相對於絕對乾燥紙漿重量)來製造面紙。將抄紙出來的面紙的單位面積重量調節為15.1g/m2 。For the raw materials of the upper layer and the lower layer, a cavitation jet type processing device (nozzle diameter: 1.5 mm) was used, and the pressure of the ejection liquid (pressure on the upstream side of the nozzle) was set to 8 MPa (measured by the instrument, and the flow rate of the jet was 80 m/sec). The pressure in the container to be sprayed (pressure on the downstream side of the nozzle) was set to 0.4 MPa (instrument measurement pressure), and two passes were performed, except that the same treatment as in Example 1 was carried out, and The Canadian standard water filtration is set to 390 ml to produce the raw material F. To the raw material F and the intermediate raw material B, 0.1% of the wet paper strength enhancer (relative to the absolute dry pulp weight) was added to produce a facial tissue. The basis weight of the paper which was taken out of paper was adjusted to 15.1 g/m 2 .
[比較例3][Comparative Example 3]
對於上層及下層的原料實施與比較例1相同的處理，將加拿大標準濾水度設定為470ml來製造出原料G。在原料G以及中層原料B中添加入濕潤紙力增強劑0.1%(相對於絕對乾燥紙漿重量)來製造面紙。將抄紙出來的面紙的單位面積重量調節為15.1g/m2 。The raw materials of the upper layer and the lower layer were treated in the same manner as in Comparative Example 1, and the Canadian standard water filtration degree was set to 470 ml to produce the raw material G. A tissue paper was prepared by adding a wet paper strength enhancer of 0.1% (relative to the absolute dry pulp weight) to the raw material G and the intermediate raw material B. The basis weight of the paper which was taken out of paper was adjusted to 15.1 g/m 2 .
如表3所示，實施例3係較之比較例3的手觸感更良好，拉伸強度高出約20%。實施例3係較之比較例3的拉伸強度大幅地提昇，但是蓬鬆度才稍微降低一點。As shown in Table 3, Example 3 showed better hand touch feeling than Comparative Example 3, and the tensile strength was about 20% higher. In Example 3, the tensile strength was greatly improved as compared with Comparative Example 3, but the bulkiness was slightly lowered.
[實施例4][Example 4]
使用具有高強度卻有手觸感不佳傾向的闊葉樹漂白牛皮紙紙漿薄片(紙漿薄片的含水率約50重量%(相對於絕對乾燥紙漿重量))來作為上層及下層的原料，除此之外，其他都進行與實施例1相同的處理，將加拿大標準濾水度設定為440ml來製造出原料H。在原料H以及中層原料B中添加入濕潤紙力增強劑0.1%(相對於絕對乾燥紙漿重量)來製造面紙。將抄紙出來的面紙的單位面積重量調節為15.1g/m2 。In addition, a broad-leaved bleached kraft pulp sheet having a high strength but a low hand touch tendency (a moisture content of the pulp sheet of about 50% by weight (relative to the absolute dry pulp weight)) is used as a raw material for the upper layer and the lower layer, in addition to The same treatment as in Example 1 was carried out, and the raw material H was produced by setting the Canadian standard water filtration degree to 440 ml. To the raw material H and the intermediate raw material B, 0.1% of the wet paper strength enhancer (relative to the absolute dry pulp weight) was added to produce a facial tissue. The basis weight of the paper which was taken out of paper was adjusted to 15.1 g/m 2 .
[比較例4][Comparative Example 4]
使用手觸感容易變好的闊葉樹漂白牛皮紙紙漿薄片(紙漿薄片的含水率約10重量%(相對於絕對乾燥紙漿重量))來作為上層及下層的原料，除此之外，其他都進行與比較例1相同的處理，將加拿大標準濾水度設定為480ml來製造出原料I。在原料I以及中層原料B中添加入濕潤紙力增強劑0.1%(相對於絕對乾燥紙漿重量)來製造面紙。將抄紙出來的面紙的單位面積重量調節為15.1g/m2 。Using a broad-leaved bleached kraft pulp sheet (the moisture content of the pulp sheet is about 10% by weight (relative to the absolute dry pulp weight)), which is easy to feel by hand, is used as a raw material for the upper layer and the lower layer, and other things are compared and compared. In the same treatment as in Example 1, the raw material I was produced by setting the Canadian standard water filtration to 480 ml. To the raw material I and the intermediate raw material B, 0.1% of the wet paper strength enhancer (relative to the absolute dry pulp weight) was added to produce a facial tissue. The basis weight of the paper which was taken out of paper was adjusted to 15.1 g/m 2 .
如表4所示，使用了具有手觸感不佳傾向的闊葉樹漂白牛皮紙紙漿的實施例4，與使用了手觸感容易變好的闊葉樹漂白牛皮紙紙漿薄片的比較例4，兩者比較之下，手觸感近乎同等程度。此外，實施例4係較之比較例4，拉伸強度提昇約40%。As shown in Table 4, Example 4 using a broad-leaved bleached kraft pulp having a tendency to feel bad to the hand, and Comparative Example 4 using a hardwood bleached kraft pulp sheet having a hand-feeling tendency to be easily improved, in comparison The touch is almost the same. Further, in Example 4, the tensile strength was improved by about 40% as compared with Comparative Example 4.
1．．．試料槽1. . . Test slot
2．．．噴嘴2. . . nozzle
3．．．氣穴現象噴流容器3. . . Cavitation phenomenon jet container
4．．．閥柱泵4. . . Valve pump
5．．．上游側壓力控制閥5. . . Upstream pressure control valve
6．．．下游側壓力控制閥6. . . Downstream pressure control valve
7．．．上游側壓力計7. . . Upstream pressure gauge
8．．．下游側壓力計8. . . Downstream side pressure gauge
9．．．供水閥9. . . Water supply valve
10．．．循環閥10. . . Circulation valve
11．．．排水閥11. . . Drain valve
12．．．溫度感應器12. . . Temperature sensor
13．．．攪拌器13. . . Blender
第1圖是本發明的實施例所使用的氣穴現象噴流式處理裝置的概略圖。Fig. 1 is a schematic view showing a cavitation flow type jet processing apparatus used in an embodiment of the present invention.
Claims (3)
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| EP (1) | EP2287396B1 (en) |
| JP (1) | JP5542356B2 (en) |
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| CA (1) | CA2717923C (en) |
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| US7967947B2 (en) | 2005-02-09 | 2011-06-28 | Nippon Paper Industries Co., Ltd. | Methods for beating pulp, methods for treating process waters, and methods for producing pulp and paper |
| CA2717923C (en) * | 2008-03-31 | 2017-04-25 | Nippon Paper Industries Co., Ltd. | Tissue papers for household use |
| JP5463985B2 (en) * | 2010-03-17 | 2014-04-09 | 株式会社リコー | Image forming apparatus |
| JP5934497B2 (en) * | 2010-12-21 | 2016-06-15 | 花王株式会社 | Tissue paper |
| US9604388B2 (en) * | 2012-02-14 | 2017-03-28 | International Paper Company | Process for making composite polymer |
| CN102578945A (en) * | 2012-02-21 | 2012-07-18 | 金红叶纸业集团有限公司 | Multi-layer living paper |
| US11124920B2 (en) | 2019-09-16 | 2021-09-21 | Gpcp Ip Holdings Llc | Tissue with nanofibrillar cellulose surface layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101115879A (en) * | 2005-02-09 | 2008-01-30 | 日本制纸株式会社 | Method for beating pulp |
| WO2007123229A1 (en) * | 2006-04-21 | 2007-11-01 | Nippon Paper Industries Co., Ltd. | Cellulose-base fibrous material |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2717923C (en) | 2017-04-25 |
| JP2009263844A (en) | 2009-11-12 |
| CA2717923A1 (en) | 2009-10-08 |
| TW201009165A (en) | 2010-03-01 |
| EP2287396A1 (en) | 2011-02-23 |
| JP5542356B2 (en) | 2014-07-09 |
| EP2287396A4 (en) | 2013-03-27 |
| WO2009122986A1 (en) | 2009-10-08 |
| CN101952505B (en) | 2013-06-05 |
| US20110011550A1 (en) | 2011-01-20 |
| EP2287396B1 (en) | 2016-03-23 |
| CN101952505A (en) | 2011-01-19 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |