JPWO2001072847A1 - Cellulose acetate and its manufacturing method - Google Patents
Cellulose acetate and its manufacturing methodInfo
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- JPWO2001072847A1 JPWO2001072847A1 JP2001-571778A JP2001571778A JPWO2001072847A1 JP WO2001072847 A1 JPWO2001072847 A1 JP WO2001072847A1 JP 2001571778 A JP2001571778 A JP 2001571778A JP WO2001072847 A1 JPWO2001072847 A1 JP WO2001072847A1
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- cellulose acetate
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- cellulose
- acetic acid
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Abstract
(57)【要約】 下記の要件（Ａ）、（Ｂ）および（Ｃ）より選んだ少なくとも１を具備することを特徴とする酢酸セルロースである。但し（Ｂ）のみを具備する場合を除く。要件（Ａ）：２０μｍ以上の輝点異物が２０個／ｍｍ３以下。要件（Ｂ）：閉塞恒数（Ｋ）が６０以下。要件（Ｃ）：測定周波数０．０１６Ｈｚの貯蔵弾性率（Ｇ’）と損失弾性率（Ｇ”）の比（Ｇ’／Ｇ”）が０．２以下。 (57) [Abstract] Cellulose acetate characterized by satisfying at least one selected from the following requirements (A), (B), and (C), except when only (B) is satisfied. Requirement (A): The number of bright spot foreign matters of 20 μm or more is 20/ mm3 or less. Requirement (B): The occlusion constant (K) is 60 or less. Requirement (C): The ratio (G'/G") of the storage modulus (G') to the loss modulus (G") at a measurement frequency of 0.016 Hz is 0.2 or less.
Description
【発明の詳細な説明】
技術分野
本発明は、溶剤に溶かしたときの微小な不溶解異物量が少なく、濾過性に優れ
た酢酸セルロース及びその製造方法に関し、特に光学用途用のフィルムの製造に
おいて、濾過漏れによりフィルムの光学的欠陥が発生するリスクを低減できる酢
酸セルロース及びその製造方法に関する。[Detailed Description of the Invention] TECHNICAL FIELD The present invention relates to a cellulose acetate that has a small amount of minute insoluble foreign matter when dissolved in a solvent and has excellent filterability, and a method for producing the same, and in particular to a cellulose acetate that can reduce the risk of optical defects in the film due to filtration leakage in the production of films for optical applications, and a method for producing the same.
更に本発明は、溶剤に溶かしたときの溶液の弾性的性質が小さく、フィルム流
延や繊維紡糸等の加工性に優れた酢酸セルロース及びその製造方法に関する。 Furthermore, the present invention relates to cellulose acetate which, when dissolved in a solvent, has a solution with small elastic properties and is excellent in processability for film casting, fiber spinning, etc., and to a method for producing the same.
更に本発明は、上記の濾過性と弾性的性質が共に改善された酢酸セルロース及
びその製造方法に関する。 The present invention further relates to cellulose acetate having improved filterability and elasticity, and a method for producing the same.
従来技術
酢酸セルロースには三酢酸セルロースと二酢酸セルロースがあり、写真用フィ
ルム、偏光板の保護フィルム、衣料用繊維、たばこフィルター用繊維束、人工腎
臓用中空繊維等の種々の用途に用いられている。PRIOR ART Cellulose acetate includes cellulose triacetate and cellulose diacetate, and is used in a variety of applications such as photographic film, protective films for polarizing plates, clothing fibers, fiber bundles for cigarette filters, and hollow fibers for artificial kidneys.
このような用途に酢酸セルロースを使用する際には、酢酸セルロースを有機溶
媒に溶解させた後、それぞれの成型体に成形する。例えば三酢酸セルロースをフ
ィルムにする場合は、酢酸セルロースをメチレンクロライド等の溶剤に溶解した
濃厚溶液（ドープ）を、鏡面状態に仕上げた支持体（ドラム、バンド等）上に流
延し、乾燥してからフィルムを剥ぎ取る、ソルトベントキャスト法が適用されて
いる。また、二酢酸セルロースを繊維にする場合は、酢酸セルロースをアセトン
等の溶剤に溶解した濃厚溶液（ドープ）を、多数の細孔を有する口金から熱風中
に吐出させ、溶媒を除去する乾式紡糸法が適用されている。 When cellulose acetate is used for such applications, it is dissolved in an organic solvent and then molded into the appropriate molded body. For example, to produce a film from cellulose triacetate, a salt vent casting method is used, in which a concentrated solution (dope) of cellulose acetate dissolved in a solvent such as methylene chloride is cast onto a mirror-finished support (drum, band, etc.), dried, and the film is peeled off. To produce fibers from cellulose diacetate, a dry spinning method is used, in which a concentrated solution (dope) of cellulose acetate dissolved in a solvent such as acetone is extruded into hot air through a nozzle with many fine holes, and the solvent is removed.
このようなフィルム流延時又は紡糸時にドープ中に溶剤に対して不溶解異物が
存在すると、成型品の品質上の問題とともに、生産上の問題を生ずる。例えば、
フィルムとして利用する場合、ドープに不溶解異物が存在すると生成したフィル
ムの光学特性（光透過率、屈折率等）に問題が生じ、繊維として利用する場合、
紡糸時に糸切れが発生し、生産性の低下を来たす。 If foreign matter insoluble in the solvent is present in the dope during film casting or spinning, problems will arise in the quality of the molded product as well as in the production process. For example,
When used as a film, the presence of insoluble foreign matter in the dope can cause problems with the optical properties (light transmittance, refractive index, etc.) of the resulting film.
Yarn breakage occurs during spinning, resulting in reduced productivity.
そこで、流延や紡糸に先立ち、ドープの濾過を行って不溶解異物を除去する処
置がなされるが、この濾過の際には、濾材の孔径が小さいほど不溶解異物の除去
効果は高くなる一方で目詰まりし易くなり、濾材の交換等で作業効率が低下する
。従って、ドープとしたときに、目詰まりの原因となる不溶解異物の少ない濾過
性に優れた酢酸セルロースが要望されている。 Therefore, prior to casting or spinning, the dope is filtered to remove insoluble foreign matters, but in this filtration, the smaller the pore size of the filter medium, the more effective it is in removing insoluble foreign matters, but the smaller the pore size of the filter medium, the more likely it is to become clogged, and the working efficiency decreases due to the need to replace the filter medium, etc. Therefore, there is a demand for cellulose acetate that has excellent filterability and contains less insoluble foreign matters that cause clogging when made into a dope.
また、偏光板保護フィルム等の光学用途においては、輝点異物は光学的欠陥の
原因となるため、特に厳しい条件の濾過が実施されるのが普通であるが、それで
も目的の不溶解物を１００％除去することは困難であり、濾過漏れが避けられな
い場合がある。このため、漏れたときのリスクをできるだけ小さくする観点から
、輝点異物の少ない酢酸セルロースが望まれている。 Furthermore, in optical applications such as polarizing plate protective films, bright spot foreign matter can cause optical defects, and therefore filtration is usually carried out under particularly strict conditions, but even with this, it is difficult to remove 100% of the target insoluble matter, and leakage during filtration is sometimes unavoidable. Therefore, from the viewpoint of minimizing the risk of leakage, cellulose acetate with fewer bright spot foreign matter is desired.
更に、酢酸セルロースを溶剤に溶かして溶液（ドープ）を作製し、そのドープ
を成型加工に供する際に、ドープの弾性的性質が大きいと、成型加工上好ましく
ない影響を及ぼすことがある。例えば、酢酸セルロースのドープからフィルムを
流延する際、ドープの弾性的性質が大きすぎると、ドープを流延バンド上に押し
出した後に、ドープ表面の十分な平滑性を得るための時間が長くなって、生産性
が低下したり、極端な場合は、十分な表面の平滑性を持ったフィルムが得られな
くなったりする。また、ドープから繊維を紡糸する際にも、ドープの弾性的性質
が大きすぎると、紡糸速度を大きくできないため、やはり生産性を低下させる。
このように主として生産性を高める観点から、ドープの弾性的性質が小さい酢酸
セルロースが望まれている。 Furthermore, when cellulose acetate is dissolved in a solvent to prepare a solution (dope) and the dope is subjected to molding, a dope with high elasticity can have undesirable effects on molding. For example, when a film is cast from a cellulose acetate dope, if the dope's elasticity is too high, it takes a long time to obtain a sufficient surface smoothness after the dope is extruded onto the casting band, resulting in a decrease in productivity, and in extreme cases, a film with a sufficient surface smoothness cannot be obtained. Furthermore, when a dope is spun into fibers, if the dope's elasticity is too high, the spinning speed cannot be increased, which also results in a decrease in productivity.
Thus, cellulose acetate having a small elasticity of the dope is desired mainly from the viewpoint of increasing productivity.
このような要望を製造工程の改善により充足せんとして、二酢酸セルロースの
製造の場合、特開昭５６−５９８０１号公報には、５０〜８５℃の高温で酢化反
応を行い、熟成工程において、１１０〜１２０℃の高温で加水分解を行う高温酢
化−高温熟成法の技術が開示されている。また、特公昭５８−２０９６１号公報
には、熟成工程において１２５〜１７０℃の高温で加水分解を行う高温熟成法が
開示されている。 In an attempt to satisfy such demands by improving the production process, Japanese Patent Laid-Open Publication No. 56-59801 discloses a high-temperature acetylation-high-temperature aging method for the production of cellulose diacetate, in which an acetylation reaction is carried out at a high temperature of 50 to 85° C. and then hydrolysis is carried out in the aging step at a high temperature of 110 to 120° C. Furthermore, Japanese Patent Publication No. 58-20961 discloses a high-temperature aging method in which hydrolysis is carried out in the aging step at a high temperature of 125 to 170° C.
しかし、成型品を先端技術分野で使用する際の品質に対する高い要求、一般消
費者の高品質指向、そして生産者の高度な生産性追求に対しては、上記した技術
では十分応えることができない。 However, the above-mentioned technologies cannot adequately meet the high quality demands for molded products used in cutting-edge technology fields, the high quality preferences of general consumers, and the high productivity demands of manufacturers.
本発明は、不溶解異物量が少なく、ドープの濾過性にも優れた酢酸セルロース
及びその製造方法の提供を課題とする。 An object of the present invention is to provide a cellulose acetate having a small amount of insoluble foreign matter and excellent filterability of the dope, and a method for producing the same.
更に本発明は、ドープの弾性的性質が小さい酢酸セルロース及びその製造方法
の提供を課題とする。 Another object of the present invention is to provide a cellulose acetate dope having small elasticity and a method for producing the same.
更に本発明は、ドープの濾過性及び弾性的性質が改善された酢酸セルロース及
びその製造方法を提供する。 The present invention also provides a cellulose acetate having improved dope filterability and elastic properties, and a method for producing the same.
発明の開示
本発明者らは、上記課題を解決する手段として、先に閉塞恒数（Ｋ）が７０以
下であるセルローストリアセテートに係わる発明を出願しており（特願平１０−
３２９１６５号明細書参照）、本発明はかかる先願発明を更に改良するものであ
る。Disclosure of the Invention As a means for solving the above problems, the present inventors have previously filed an invention relating to cellulose triacetate having a blocking constant (K) of 70 or less (Japanese Patent Application No. 10-2004).
The present invention is a further improvement over the prior invention.
本発明者らは、酢酸セルロースを溶剤に溶かしたドープの不溶解異物について
詳細に分析検討した結果、ドープから製膜したフィルムを偏光顕微鏡下で見たと
き輝点異物として観察される不溶解異物の量が濾材の目詰りと高い相関を示すこ
と、輝点異物は反応が不十分なセルロース繊維が崩壊した微細フラグメントであ
り、このような微細フラグメントを酢化反応系内に混入させないことによって、
ドープ中の不溶解異物量を大幅に減少できることを見出し、本発明を完成した。 The present inventors have conducted a detailed analysis and investigation of insoluble foreign matter in a dope prepared by dissolving cellulose acetate in a solvent. As a result, they have found that the amount of insoluble foreign matter observed as bright spots when a film made from the dope is viewed under a polarizing microscope is highly correlated with the clogging of the filter medium, and that the bright spots are fine fragments formed by the breakdown of insufficiently reacted cellulose fibers. By preventing such fine fragments from being mixed into the acetylation reaction system,
The inventors have found that the amount of insoluble foreign matter in the dope can be significantly reduced, and have completed the present invention.
本発明は、下記の要件（Ａ）、（Ｂ）および（Ｃ）より選んだ少なくとも１を
具備することを特徴とする酢酸セルロース、但し（Ｂ）のみを具備する場合を除
く。 The present invention relates to a cellulose acetate characterized by satisfying at least one of the following requirements (A), (B) and (C), except that only requirement (B) is satisfied.
要件（Ａ）：２０μｍ以上の輝点異物が２０個／ｍｍ３以下。 Requirement (A): The number of bright foreign particles of 20 μm or more is 20 or less per mm3 .
（輝点異物の測定方法）
酢酸セルロースをメチレンクロライド／メタノール＝９／１（重量比）混合溶
媒に溶解し、１５重量％（固形分濃度）の溶液（ドープ）を得る。このドープを
スライドグラス上に流延、乾燥し、スライドグラス上に厚さ１００μｍ程度のフ
ィルム状のサンプルを得る。このサンプルを偏光顕微鏡で暗視野下で観察し、面
積３２ｍｍ２内にある最大長さが２０μｍ以上の輝点異物を数え、別途測定した
正確なフィルムの厚みで補正し、単位体積（１ｍｍ３）あたりの異物数を求める
。異なるドープから製膜したフィルム３枚について同様の測定を行い、それらの
平均値を算出し、輝点異物の数とする。(Method for measuring bright spots) Cellulose acetate is dissolved in a mixed solvent of methylene chloride/methanol = 9/1 (weight ratio) to obtain a 15 wt% (solid content concentration) solution (dope). This dope is cast onto a slide glass and dried to obtain a film-like sample on the slide glass with a thickness of approximately 100 μm. This sample is observed under a polarizing microscope in a dark field, and bright spots with a maximum length of 20 μm or more within an area of 32 mm2 are counted, and the number of foreign particles per unit volume (1 mm3 ) is calculated by correcting for the accurate film thickness measured separately. Similar measurements are performed on three films formed from different dopes, and the average value is calculated to obtain the number of bright spots.
要件（Ｂ）：閉塞恒数（Ｋ）が６０以下。Requirement (B): The blocking constant (K) is 60 or less.
（閉塞恒数の測定方法）
酢酸セルロースをメチレンクロライド／メタノール＝９／１（重量比）混合溶
媒に溶解し、１６重量％（固形分濃度）の溶液を得る。この溶液を金巾濾材を使
用して濾過圧力２９４ｋＰａ（３ｋｇ／ｃｍ２）、温度２５℃で定圧濾過し、経
時的に測定した濾過量からｔ／Ｖ〜ｔ［ｔは濾過時間（分）、Ｖは濾過量（ｍｌ
）を示す〕で表される直線の勾配を算出し、Ｋ＝勾配×２×１０４から閉塞恒数
（Ｋ）を求める。(Method for measuring the blocking constant) Cellulose acetate was dissolved in a mixed solvent of methylene chloride/methanol = 9/1 (weight ratio) to obtain a 16 wt% (solid content concentration) solution. This solution was filtered using a gold filter medium at a constant pressure of 294 kPa (3 kg/ cm2 ) and a temperature of 25°C, and t/V-t (t is the filtration time (min), V is the filtration volume (ml)) was calculated from the filtration volume measured over time.
The gradient of the straight line represented by the formula is calculated, and the occlusion constant (K) is calculated from K = gradient × 2 × 10 4 .
要件（Ｃ）：測定周波数０．０１６Ｈｚの貯蔵弾性率（Ｇ’）と損失弾性率（
Ｇ”）の比（Ｇ’／Ｇ”）が０．２以下。 Requirement (C): Storage modulus (G') and loss modulus (
The ratio (G'/G") of the total strength of the polymer (polymer) to the total strength of the polymer (polymer) (polymer) (polymer) is 0.2 or less.
（動的粘弾性の測定方法）
酢酸セルロース１５．５重量部、トリフェニルホスフェイト１．５重量部及び
ビフェニルジフェニルホスフェイト０．９重量部をメチレンクロライド６９．８
重量部とメタノール１２．３重量部に溶解した溶液を作製する。この溶液の動的
粘弾性（Ｇ’とＧ”）を２５℃で測定する。Ｐａａｒ Ｐｈｙｓｉｃａ社製 粘
弾性測定装置ＵＤＳ２００を用いることができる。(Method for measuring dynamic viscoelasticity) 15.5 parts by weight of cellulose acetate, 1.5 parts by weight of triphenyl phosphate, and 0.9 parts by weight of biphenyl diphenyl phosphate were dissolved in 69.8 parts by weight of methylene chloride.
A solution is prepared by dissolving 1 part by weight of the polymer in 12.3 parts by weight of methanol. The dynamic viscoelasticity (G' and G") of this solution is measured at 25°C. A viscoelasticity measuring device UDS200 manufactured by Paar Physica can be used.
本発明には、（Ａ）及び（Ｂ）、（Ａ）及び（Ｃ）あるいは（Ｂ）及び（Ｃ）
を具備する酢酸セルロースを含む。さらに要件（Ｃ）を具備する酢酸セルロース
、要件（Ａ）、（Ｂ）及び（Ｃ）を具備する酢酸セルロースも含む。 The present invention includes (A) and (B), (A and (C), or (B and (C)
It further includes cellulose acetate satisfying requirement (C) and cellulose acetate satisfying requirements (A), (B) and (C).
要件（Ａ）の２０μｍ以上の輝点異物が１０個／ｍｍ３以下であることが好ま
しい。（Ｃ）のＧ’／Ｇ”が０．１以下であることも好ましい。さらに（Ｃ）の
Ｇ’／Ｇ”が０．０６以下であることも好ましい。 It is preferable that the number of bright foreign particles of 20 μm or more in requirement (A) is 10/ mm3 or less. It is also preferable that G'/G" in (C) is 0.1 or less. It is further preferable that G'/G" in (C) is 0.06 or less.
本発明は、セルロースを酢酸で処理する前処理工程、前処理セルロースを酢化
反応系に送る送綿工程及び酢化反応工程を含む酢酸セルロースの製造方法におい
て、送綿工程の送綿経路に付着した前処理セルロースを、酢化反応開始に先立ち
酢酸又は酢酸と無水酢酸混合液で酢化反応系内へ洗い落とすことを特徴とする上
記の酢酸セルロースの製造方法も提供する。 The present invention also provides a method for producing cellulose acetate, which comprises a pretreatment step of treating cellulose with acetic acid, a feeding step of feeding the pretreated cellulose to an acetylation reaction system, and an acetylation reaction step, characterized in that the pretreated cellulose adhering to the feeding path in the feeding step is washed off into the acetylation reaction system with acetic acid or a mixture of acetic acid and acetic anhydride prior to the start of the acetylation reaction.
洗浄に用いる酢酸又は酢酸と無水酢酸混合液の使用量が、原料セルロース１０
０重量部に対し５〜５０容量部であることが好ましい。 The amount of acetic acid or the mixture of acetic acid and acetic anhydride used for washing is 100% of the raw material cellulose.
It is preferable that the amount is 5 to 50 parts by volume per 0 part by weight.
本発明における酢酸セルロースは、三酢酸セルロース及び／又は二酢酸セルロ
ースを意味するものである。 The cellulose acetate in the present invention means cellulose triacetate and/or cellulose diacetate.
発明の実施の形態
本発明の酢酸セルロースは、上記方法により求められる要件（Ａ）〜（Ｃ）を
、要件（Ａ）、要件（Ａ）及び（Ｂ）、要件（Ｃ）又は要件（Ａ）、（Ｂ）及び
（Ｃ）の組合せで具備するものである。Modes for Carrying Out the Invention The cellulose acetate of the present invention satisfies the requirements (A) to (C) required by the above-mentioned method in the form of a combination of requirement (A), requirements (A) and (B), requirement (C), or requirements (A), (B), and (C).
要件（Ａ）の２０μｍ以上の輝点異物は、２０個／ｍｍ３以下、好ましくは１
０個／ｍｍ３以下である。 The number of bright foreign particles of 20 μm or more in requirement (A) is 20/ mm3 or less, preferably 1
0 particles/ mm3 or less.
要件（Ｂ）の閉塞恒数（Ｋ）は、６０以下、好ましくは５０以下である。The blocking constant (K) of requirement (B) is 60 or less, preferably 50 or less.
要件（Ｃ）の測定周波数０．０１６Ｈｚの貯蔵弾性率（Ｇ’）と損失弾性率（
Ｇ”）の比（Ｇ’／Ｇ”）は、０．２以下、好ましくは０．１以下、より好まし
くは０．０６以下である。 Requirement (C) Measurement frequency of 0.016 Hz Storage modulus (G') and loss modulus (
The ratio (G'/G") of the thickness of the polymer to the thickness of the polymer (G") is 0.2 or less, preferably 0.1 or less, and more preferably 0.06 or less.
要件（Ａ）又は要件（Ａ）及び（Ｂ）を具備することによって、濾過性が向上
し、例えば紡糸工程において不都合な異物を濾過により除去することが容易にな
る。特に輝点異物の数を少なくすることで、偏光板保護フィルム等の光学用途に
適用した場合、濾過漏れの場合のリスクも小さくできる。 By satisfying requirement (A) or requirements (A) and (B), filterability is improved, and it becomes easier to remove unwanted foreign matter by filtration, for example, during the spinning process. In particular, by reducing the number of bright spot foreign matter, the risk of filtration leakage can be reduced when the film is used in optical applications such as polarizing plate protective films.
要件（Ｃ）を具備することによって、ドープの弾性的性質を小さく抑えること
ができるので、フィルムの流延及び紡糸速度を上げて生産性を高めることができ
る。 By satisfying the requirement (C), the elasticity of the dope can be suppressed to a small value, and therefore the film casting and spinning speeds can be increased, thereby improving productivity.
要件（Ａ）、（Ｂ）及び（Ｃ）を具備することによって、上記した作用効果を
得ることができる。 By satisfying the requirements (A), (B) and (C), the above-mentioned effects can be obtained.
次に、本発明の酢酸セルロースの製造法について説明する。本発明の酢酸セル
ロースの製造方法は、前処理セルロースを酢化反応工程へ送る送綿工程に特徴を
有するものであり、この送綿工程の前後に行う工程処理については、一般的な酢
酸セルロースの製造工程の処理を適用できる。以下において、本発明の酢酸セル
ロースの製造方法を工程ごとに順に説明する。 Next, the method for producing cellulose acetate of the present invention will be described. The method for producing cellulose acetate of the present invention is characterized by a feeding step in which pretreated cellulose is sent to an acetylation reaction step. Treatments performed before and after this feeding step can be those typically used in the production of cellulose acetate. Each step of the method for producing cellulose acetate of the present invention will be described below in order.
まず、原料となる木材パルプ等の解砕セルロースに酢酸を添加して前処理活性
化する。この前処理活性化における酢酸の使用量は、セルロース１００重量部に
対して、好ましくは１０〜５００重量部である。また、前処理活性化は、好まし
くは密閉及び攪拌条件下、２０〜５０℃で、０．５〜２時間行う。 First, acetic acid is added to the raw material, disintegrated cellulose such as wood pulp, to pre-activate it. The amount of acetic acid used in this pre-activation is preferably 10 to 500 parts by weight per 100 parts by weight of cellulose. The pre-activation is preferably carried out under sealed and agitated conditions at 20 to 50°C for 0.5 to 2 hours.
次に、送綿工程の処理を行う。この工程においては、前処理セルロースを酢化
反応系に送るとともに、送綿経路に付着した前処理セルロースを酢化反応系に洗
い落とす（洗浄する）処理をする。 Next, the pretreated cellulose is sent to an acetylation reaction system, and the pretreated cellulose adhering to the acetylation reaction system is washed off (cleaned) in the acetylation reaction system.
送綿工程の送綿経路を形成する送綿装置は、好ましくは内部に１又は２個のダ
ンパーを有するものであり、その他、１又は２以上の液体噴霧ノズル等の液体噴
霧手段を具備したダクトも適用できる。 The cotton feeding device that forms the cotton feeding path in the cotton feeding process preferably has one or two dampers inside, and a duct equipped with one or more liquid spray means such as a liquid spray nozzle can also be used.
送綿工程で使用する洗浄液となる酢酸又は酢酸−無水酢酸混合液において、酢
酸の場合は氷酢酸が使用され、酢酸−無水酢酸混合液の場合は、酢酸と無水酢酸
の割合が重量比で好ましくは１：９９〜９９：１、より好ましくは４０：６０〜
６０：４０の混合液が使用される。 In the acetic acid or acetic acid-acetic anhydride mixture used as the cleaning solution in the cotton-feeding process, glacial acetic acid is used in the case of acetic acid, and in the case of acetic acid-acetic anhydride mixture, the weight ratio of acetic acid to acetic anhydride is preferably 1:99 to 99:1, more preferably 40:60 to 60:1.
A 60:40 mixture is used.
洗浄液量は、使用したセルロース１００重量部に対して、好ましくは５〜５０
容量部、より好ましくは１０〜５０容量部、更に好ましくは１５〜５０容量部で
ある。５容量部以上であると、付着した前処理セルロースの洗浄による落下効果
が高く、５０容量部以下であると洗浄時間が長くなり過ぎることが防止される。 The amount of the washing liquid is preferably 5 to 50 parts by weight based on 100 parts by weight of the cellulose used.
The volumetric amount is preferably 5 parts by volume, more preferably 10 to 50 parts by volume, and even more preferably 15 to 50 parts by volume. When the volumetric amount is 5 parts by volume or more, the effect of removing the adhering pretreated cellulose by washing is high, and when the volumetric amount is 50 parts by volume or less, the washing time is prevented from becoming too long.
洗浄液の温度は、好ましくは１５〜５０℃、より好ましくは１５〜４０℃、更
に好ましくは１５〜３０℃である。 The temperature of the cleaning solution is preferably 15 to 50°C, more preferably 15 to 40°C, and even more preferably 15 to 30°C.
洗浄方法は、送綿経路に付着した前処理セルロースを洗い落とすことができる
方法であれば特に限定されず、洗浄液を噴霧する方法、洗浄液をシャワー状に注
入する方法等を適用することができる。 The cleaning method is not particularly limited as long as it can wash off the pretreated cellulose adhering to the cotton feeding path, and methods such as spraying a cleaning liquid or injecting the cleaning liquid in a shower can be applied.
次に、酢化反応工程の処理を行う。酢化反応工程における無水酢酸と酢酸の使
用量は、前記送綿工程で添加する酢酸又は酢酸−無水酢酸混合液量も含め、セル
ロース１００重量部に対して、無水酢酸が好ましくは２００〜４００重量部、よ
り好ましくは２４０〜２８０重量部であり、酢酸が好ましくは３００〜６００重
量部、より好ましくは３５０〜５００重量部である。 The amounts of acetic anhydride and acetic acid used in the acetylation reaction step, including the amount of acetic acid or the acetic acid-acetic anhydride mixture added in the fiber-feeding step, are preferably 200 to 400 parts by weight, more preferably 240 to 280 parts by weight, and preferably 300 to 600 parts by weight, more preferably 350 to 500 parts by weight, of acetic acid per 100 parts by weight of cellulose.
触媒としての硫酸の添加量は、セルロース１００重量部に対して、好ましくは
５〜１５重量部である。 The amount of sulfuric acid added as a catalyst is preferably 5 to 15 parts by weight per 100 parts by weight of cellulose.
酢化反応は、上記反応剤を添加した後、攪拌条件下、４０〜９０分かけ、ほぼ
一定速度で昇温しながら、最終的に３０〜５５℃で１５〜６０分間保持して行う
ことが望ましい。 After adding the reactants, the acetylation reaction is preferably carried out under stirring conditions by raising the temperature at a substantially constant rate over 40 to 90 minutes, and ultimately maintaining the temperature at 30 to 55°C for 15 to 60 minutes.
次に、熟成工程の処理を行う。この熟成処理は、酢化反応生成系中の硫酸触媒
を、完全又は一部中和し、系内の温度を５０〜１５０℃とし、同温度範囲で１５
分〜２時間保持して、所望の酢化度の酢酸セルロースを得る。 Next, the aging step is carried out. In this aging treatment, the sulfuric acid catalyst in the acetylation reaction system is completely or partially neutralized, the temperature in the system is set to 50 to 150°C, and the mixture is left for 15 minutes at this temperature range.
The mixture is kept for 1 minute to 2 hours to obtain cellulose acetate with the desired degree of acetylation.
次に、反応混合物を稀酢酸水溶液中に投入し、沈殿物として回収し、水洗、乾
燥して製品とする。 Next, the reaction mixture is poured into a dilute aqueous solution of acetic acid, and the precipitate is recovered, washed with water, and dried to obtain the product.
本発明の製造方法は、三酢酸セルロース及び二酢酸セルロースの製造のいずれ
にも高い効果があるが、三酢酸セルロースの製造において特に効果が高い。 The production method of the present invention is highly effective for the production of both cellulose triacetate and cellulose diacetate, but is particularly effective for the production of cellulose triacetate.
本発明の酢酸セルロースは、要件（Ａ）、（Ｂ）及び（Ｃ）を所定の組合せで
具備することにより、濾過性、輝点異物の数、ドープの弾性的性質等を改善する
ことができる。このため、例えばフィルム用途に利用する場合、光学的に高い性
能を示すフィルムを安定して製造できるようになる。 The cellulose acetate of the present invention, which satisfies the requirements (A), (B), and (C) in a predetermined combination, can improve filterability, the number of bright spot foreign matters, the elastic properties of the dope, etc. Therefore, when used in film applications, for example, films exhibiting high optical performance can be stably produced.
本発明の製造方法は、前記した酢酸セルロースを工業的に安定に製造すること
ができる。 The production method of the present invention enables the above-mentioned cellulose acetate to be produced industrially and stably.
実施例
以下に本発明を具体的に説明する実施例を示すが、本発明は以下に示す実施例
に限定されるものではない。また、酢酸セルロースの物性測定は次の方法で行っ
た。EXAMPLES The following examples are provided to specifically explain the present invention, but the present invention is not limited to the examples shown below. The physical properties of cellulose acetate were measured by the following methods.
（１）酢化度
酢化度は、ＡＳＴＭ：Ｄ−８１７−９１（セルロースアセテートなどの試験方
法）の酢化度の測定法に準じて測定した。まず、乾燥した酢酸セルロース１．９
ｇを精秤し、アセトンとジメチルスルホキシドとの混合溶媒（容量比４：１）１
５０ｍｌに溶解した後、１Ｎ−水酸化ナトリウム水溶液３０ｍｌを添加し、２５
℃で２時間ケン化する。次に、フェノールフタレイン溶液を指示薬として添加し
、１Ｎ−硫酸で過剰の水酸化ナトリウムを滴定した後、下記式にしたがって酢化
度を算出する。なお、同様の方法により、ブランク試験を行う。(1) Acetyl group content The acetyl group content was measured in accordance with the method for measuring acetyl group content of ASTM D-817-91 (testing method for cellulose acetate, etc.). First, dried cellulose acetate 1.9
g was weighed out and dissolved in 1 g of a mixed solvent of acetone and dimethyl sulfoxide (volume ratio 4:1).
After dissolving in 50 ml of water, 30 ml of 1N sodium hydroxide solution was added, and the mixture was stirred for 25 minutes.
Saponify at 20°C for 2 hours. Next, add phenolphthalein solution as an indicator, titrate excess sodium hydroxide with 1N sulfuric acid, and calculate the degree of acetylation according to the following formula. A blank test is also conducted in the same manner.
酢化度（％）＝〔６．００５×（Ｂ−Ａ）×Ｆ］／Ｗ
（式中、Ａは試料の滴定に要した１Ｎ−硫酸のｍｌ数、Ｂはブランク試験の滴定
に要した１Ｎ−硫酸のｍｌ数、Ｆは１Ｎ−硫酸の濃度ファクター、Ｗは試料重量
を示す。）
（２）６％粘度
三角フラスコに乾燥試料６．０ｇ、メチレンクロライド／メタノール＝９１／
９（重量比）混合溶媒９４．０ｍｌを入れ、密栓して約１時間攪拌した。その後
、回転振盪機で約１時間振盪して完溶させた。得られた６ｗｔ／ｖｏｌ％の溶液
を所定オストワルド粘度計の標線まで移し、２５±１℃で約３０分間整温した。
計時標線間の流下時間を測定し、次式により６％粘度を算出した。Acetyl group content (%) = [6.005 x (B - A) x F] / W (where A is the number of ml of 1N sulfuric acid required to titrate the sample, B is the number of ml of 1N sulfuric acid required to titrate the blank test, F is the concentration factor of 1N sulfuric acid, and W is the weight of the sample.) (2) 6% viscosity: 6.0 g of dried sample was placed in an Erlenmeyer flask and a 91:9 ratio of methylene chloride/methanol was added.
94.0 ml of a 9 (weight ratio) mixed solvent was added, sealed, and stirred for approximately 1 hour. The container was then shaken for approximately 1 hour on a rotary shaker to completely dissolve the solution. The resulting 6 wt/vol% solution was poured up to the marked line on an Ostwald viscometer and allowed to warm to 25±1°C for approximately 30 minutes.
The flow time between the time marks was measured, and the 6% viscosity was calculated using the following formula.
６％粘度（ｍＰａｓ）＝流下時間（ｓ）×粘度計係数
粘度計係数は、粘度計校正用標準液を用いて上記と同様の操作で流下時間を測
定し、次式より求めた。6% viscosity (mPas) = flow time (s) x viscometer coefficient The viscometer coefficient was calculated from the following formula by measuring the flow time in the same manner as above using a standard solution for calibrating a viscometer.
（３）不溶解物量
メチレンクロライド：メタノール＝９：１（重量比）溶液に、２％固形分濃度
になるよう酢酸セルロースを溶解した溶液（ドープ）を、ガラスフィルター（Ｇ
−４：孔径５〜１０μｍ、相互理化学硝子製作所製）を使用して濾過する。その
後、濾過残渣に付着しているドープをメチレンクロライド：メタノール＝９：１
（重量比）溶液で十分洗浄除去する。濾過残渣をガラスフィルターごと恒量にな
るまで乾燥する。濾過前後のガラスフィルター重量を測定し、次式より不溶解物
量を算出する。 (3) Amount of insoluble matter A solution (dope) in which cellulose acetate was dissolved in a methylene chloride:methanol=9:1 (weight ratio) solution to a solid content of 2% was filtered through a glass filter (G
The dope adhering to the filtration residue was removed by filtration using a filtration tube (pore size 5-10 μm, manufactured by Sogo Rikagaku Glass Manufacturing Co., Ltd.).
The residue is thoroughly washed with a (weight ratio) solution. The glass filter is dried until it reaches a constant weight. The weight of the glass filter is measured before and after filtration, and the amount of insoluble matter is calculated using the following formula.
実施例１
セルロースパルプ１００重量部に氷酢酸５０重量部を散布して、前処理活性化
した。この前処理セルロースを酢化機に送綿した後、氷酢酸１０容量部で送綿装
置内部に付着している前処理セルロースを酢化機へ洗い落とした。その後、氷酢
酸４１０重量部、無水酢酸２６０重量部、硫酸８重量部を添加し酢化処理を行っ
た。 Example 1: 100 parts by weight of cellulose pulp was pretreated and activated by spraying 50 parts by weight of glacial acetic acid. This pretreated cellulose was fed to an acetylation machine, and the pretreated cellulose adhering to the inside of the feeding device was washed off into the acetylation machine with 10 parts by volume of glacial acetic acid. Then, 410 parts by weight of glacial acetic acid, 260 parts by weight of acetic anhydride, and 8 parts by weight of sulfuric acid were added to carry out an acetylation treatment.
酢化終了後、酢酸マグネシウム１５重量％酢酸−水混合溶液を、溶液中の水の
濃度が３．０重量％、硫酸イオン濃度が０．５重量％になるまで添加して無水酢
酸を分解させ、酢化反応を停止し、系内に過熱蒸気を吹き込み、温度と時間を調
整し熟成を行った。その後、常法により精製・乾燥し、フレーク状酢酸セルロー
スを得た。 After the completion of the acetylation, a 15 wt % magnesium acetate acetic acid-water mixed solution was added until the water concentration in the solution became 3.0 wt % and the sulfate ion concentration became 0.5 wt % to decompose the acetic anhydride, and the acetylation reaction was stopped. Superheated steam was blown into the system, and aging was carried out by adjusting the temperature and time. Thereafter, the product was purified and dried by a conventional method to obtain flaky cellulose acetate.
実施例２
セルロースパルプ１００重量部に氷酢酸５０重量部を散布して、前処理活性化
した。この前処理セルロースを酢化機に送綿した後、氷酢酸１０容量部で送綿装
置内部に付着している前処理セルロースを酢化機へ洗い落とした。その後、氷酢
酸４１０重量部、無水酢酸２６０重量部、硫酸８重量部を添加し酢化処理を行っ
た。Example 2: Cellulose pulp was pretreated and activated by spraying 50 parts by weight of glacial acetic acid onto 100 parts by weight. This pretreated cellulose was fed into an acetylation machine, and the pretreated cellulose adhering to the inside of the feeding device was washed off into the acetylation machine with 10 parts by volume of glacial acetic acid. Then, 410 parts by weight of glacial acetic acid, 260 parts by weight of acetic anhydride, and 8 parts by weight of sulfuric acid were added to carry out the acetylation treatment.
酢化終了後、酢酸マグネシウム１５重量％酢酸−水混合溶液を、溶液中の水の
濃度が３．０重量％、硫酸イオン濃度が０．５重量％になるまで添加して無水酢
酸を分解させ、酢化反応を停止し、停止時の水と無水酢酸の反応熱で上昇する温
度で所定時間熟成を行った。その後、常法により精製・乾燥し、フレーク状酢酸
セルロースを得た。 After the acetylation reaction was completed, a 15 wt % magnesium acetate acetic acid-water mixed solution was added until the water concentration in the solution reached 3.0 wt % and the sulfate ion concentration reached 0.5 wt % to decompose the acetic anhydride, and the acetylation reaction was terminated. The mixture was then aged for a predetermined time at a temperature increased by the heat of reaction between water and acetic anhydride at the time of terminating the reaction. Thereafter, the mixture was purified and dried by a conventional method to obtain flaky cellulose acetate.
実施例３
セルロースパルプ１００重量部に氷酢酸５０重量部を散布して、前処理活性化
した。この前処理セルロースを酢化機に送綿した後、氷酢酸１５容量部で送綿装
置内部に付着している前処理セルロースを酢化機へ洗い落とした。その後、氷酢
酸４０．５重量部、無水酢酸２６０重量部、硫酸８重量部を添加し酢化処理を行
った。Example 3: Cellulose pulp was pretreated and activated by spraying 50 parts by weight of glacial acetic acid onto 100 parts by weight. This pretreated cellulose was fed into an acetylation machine, and the pretreated cellulose adhering to the inside of the feeding device was washed off into the acetylation machine with 15 parts by volume of glacial acetic acid. Then, 40.5 parts by weight of glacial acetic acid, 260 parts by weight of acetic anhydride, and 8 parts by weight of sulfuric acid were added to carry out the acetylation treatment.
酢化終了後、酢酸マグネシウム１５重量％酢酸−水混合溶液を、溶液中の水の
濃度が３．０重量％、硫酸イオン濃度が０．５重量％になるまで添加して無水酢
酸を分解させ、酢化反応を停止し、系内に過熱蒸気を吹き込み、温度と時間を調
整し熟成を行った。その後、常法により精製・乾燥し、フレーク状酢酸セルロー
スを得た。 After the completion of the acetylation, a 15 wt % magnesium acetate acetic acid-water mixed solution was added until the water concentration in the solution became 3.0 wt % and the sulfate ion concentration became 0.5 wt % to decompose the acetic anhydride, and the acetylation reaction was stopped. Superheated steam was blown into the system, and aging was carried out by adjusting the temperature and time. Thereafter, the product was purified and dried by a conventional method to obtain flaky cellulose acetate.
実施例４
セルロースパルプ１００重量部に氷酢酸５０重量部を散布して、前処理活性化
した。この前処理セルロースを酢化機に送綿した後、氷酢酸１５容量部で送綿装
置内部に付着している前処理セルロースを酢化機へ洗い落とした。その後、氷酢
酸４０５重量部、無水酢酸２６０重量部、硫酸８重量部を添加し酢化処理を行っ
た。Example 4: Cellulose pulp was pretreated and activated by spraying 50 parts by weight of glacial acetic acid onto 100 parts by weight. This pretreated cellulose was fed into an acetylation machine, and the pretreated cellulose adhering to the inside of the feeding device was washed off into the acetylation machine with 15 parts by volume of glacial acetic acid. Then, 405 parts by weight of glacial acetic acid, 260 parts by weight of acetic anhydride, and 8 parts by weight of sulfuric acid were added to carry out the acetylation treatment.
酢化終了後、酢酸マグネシウム１５重量％酢酸−水混合溶液を、溶液中の水の
濃度が３．０重量％、硫酸イオン濃度が０．５重量％になるまで添加して無水酢
酸を分解させ、酢化反応を停止し、停止時の水と無水酢酸の反応熱で上昇する温
度で所定時間熟成を行った。その後、常法により精製・乾燥し、フレーク状酢酸
セルロースを得た。 After the completion of the acetylation, a 15 wt % magnesium acetate acetic acid-water mixed solution was added until the water concentration in the solution became 3.0 wt % and the sulfate ion concentration became 0.5 wt % to decompose the acetic anhydride, and the acetylation reaction was terminated. The mixture was then aged for a predetermined time at a temperature increased by the heat of reaction between water and acetic anhydride at the time of terminating the reaction. Thereafter, the mixture was purified and dried by a conventional method to obtain flaky cellulose acetate.
実施例５
セルロースパルプ１００重量部に氷酢酸５０重量部を散布して、前処理活性化
した。この前処理セルロースを酢化機に送綿した後、氷酢酸／無水酢酸５０／５
０（重量比）の混合液２０容量部で送綿装置内部に付着している前処理セルロー
スを酢化機へ洗い落とした。その後、氷酢酸４１０重量部、無水酢酸２５０重量
部、硫酸８重量部を添加し酢化処理を行った。Example 5 100 parts by weight of cellulose pulp was sprayed with 50 parts by weight of glacial acetic acid to perform pretreatment and activation. This pretreated cellulose was sent to an acetylation machine and then treated with a 50/50 mixture of glacial acetic acid and acetic anhydride.
The pretreated cellulose adhering to the inside of the cotton-feeding device was washed off into the acetylation machine with 20 parts by volume of a mixture of 20 parts by volume of cellulose acetate and 10 parts by volume of acetic anhydride (weight ratio). Then, 410 parts by weight of glacial acetic acid, 250 parts by weight of acetic anhydride, and 8 parts by weight of sulfuric acid were added to carry out the acetylation treatment.
酢化終了後、酢酸マグネシウム１５重量％酢酸−水混合溶液を、溶液中の水の
濃度が３．０重量％、硫酸イオン濃度が０．５重量％になるまで添加して無水酢
酸を分解させ、酢化反応を停止し、停止時の水と無水酢酸の反応熱で上昇する温
度で所定時間熟成を行った。その後、常法により精製・乾燥し、フレーク状酢酸
セルロースを得た。 After the acetylation reaction was completed, a 15 wt % magnesium acetate acetic acid-water mixed solution was added until the water concentration in the solution reached 3.0 wt % and the sulfate ion concentration reached 0.5 wt % to decompose the acetic anhydride, and the acetylation reaction was terminated. The mixture was then aged for a predetermined time at a temperature increased by the heat of reaction between water and acetic anhydride at the time of terminating the reaction. Thereafter, the mixture was purified and dried by a conventional method to obtain flaky cellulose acetate.
実施例６
セルロースパルプ１００重量部に氷酢酸５０重量部を散布して、前処理活性化
した。この前処理セルロースを酢化機に送綿した後、氷酢酸／無水酢酸６０／４
０（重量比）の混合液３０容量部で送綿装置内部に付着している前処理セルロー
スを酢化機へ洗い落とした。その後、氷酢酸４００重量部、無水酢酸２５０重量
部、硫酸８重量部を添加し酢化処理を行った。Example 6 100 parts by weight of cellulose pulp was sprayed with 50 parts by weight of glacial acetic acid to perform pretreatment and activation. This pretreated cellulose was sent to an acetylation machine and then treated with a 60/4 mixture of glacial acetic acid and acetic anhydride.
The pretreated cellulose adhering to the inside of the cotton-feeding device was washed off into the acetylation machine with 30 parts by volume of a mixture of 100 parts by weight of glacial acetic acid, 250 parts by weight of acetic anhydride, and 8 parts by weight of sulfuric acid, and the acetylation treatment was then carried out.
酢化終了後、酢酸マグネシウム１５重量％酢酸−水混合溶液を、溶液中の水の
濃度が３．０重量％、硫酸イオン濃度が０．５重量％になるまで添加して無水酢
酸を分解させ、酢化反応を停止し、系内に過熱蒸気を吹き込み、温度と時間を調
整し熟成を行った。その後、常法により精製・乾燥し、フレーク状酢酸セルロー
スを得た。 After the completion of the acetylation, a 15 wt % magnesium acetate acetic acid-water mixed solution was added until the water concentration in the solution became 3.0 wt % and the sulfate ion concentration became 0.5 wt % to decompose the acetic anhydride, and the acetylation reaction was stopped. Superheated steam was blown into the system and aging was carried out by adjusting the temperature and time. Thereafter, the product was purified and dried by a conventional method to obtain flaky cellulose acetate.
実施例７
セルロースパルプ１００重量部に氷酢酸５０重量部を散布して、前処理活性化
した。この前処理セルロースを酢化機に送綿した後、氷酢酸／無水酢酸６０／４
０（重量比）の混合液３０容量部で送綿装置内部に付着している前処理セルロー
スを酢化機へ洗い落とした。その後、氷酢酸４００重量部、無水酢酸２５０重量
部、硫酸８重量部を添加し酢化処理を行った。Example 7 100 parts by weight of cellulose pulp was sprayed with 50 parts by weight of glacial acetic acid to perform pretreatment and activation. This pretreated cellulose was sent to an acetylation machine and then treated with a 60/4 mixture of glacial acetic acid and acetic anhydride.
The pretreated cellulose adhering to the inside of the cotton-feeding device was washed off into the acetylation machine with 30 parts by volume of a mixture of 100 parts by weight of glacial acetic acid, 250 parts by weight of acetic anhydride, and 8 parts by weight of sulfuric acid, and the acetylation treatment was then carried out.
酢化終了後、酢酸マグネシウム１５重量％酢酸−水混合溶液を、溶液中の水の
濃度が３．０重量％、硫酸イオン濃度が０．５重量％になるまで添加して無水酢
酸を分解させ、酢化反応を停止し、停止時の水と無水酢酸の反応熱で上昇する温
度で所定時間熟成を行った。その後、常法により精製・乾燥し、フレーク状酢酸
セルロースを得た。 After the acetylation reaction was completed, a 15 wt % magnesium acetate acetic acid-water mixed solution was added until the water concentration in the solution reached 3.0 wt % and the sulfate ion concentration reached 0.5 wt % to decompose the acetic anhydride, and the acetylation reaction was terminated. The mixture was then aged for a predetermined time at a temperature increased by the heat of reaction between water and acetic anhydride at the time of terminating the reaction. Thereafter, the mixture was purified and dried by a conventional method to obtain flaky cellulose acetate.
比較例１
セルロースパルプ１００重量部に氷酢酸５０重量部を散布して、前処理活性化
した。この前処理セルロースを酢化機に送綿した後、送綿装置内部に付着してい
る前処理セルロースを酢化機へ洗い落とすことなく、氷酢酸４２０重量部、無水
酢酸２６０重量部、硫酸８重量部を添加し酢化処理を行った。Comparative Example 1: 100 parts by weight of cellulose pulp was sprayed with 50 parts by weight of glacial acetic acid for pretreatment activation. This pretreated cellulose was fed to an acetylation machine, and then 420 parts by weight of glacial acetic acid, 260 parts by weight of acetic anhydride, and 8 parts by weight of sulfuric acid were added to carry out acetylation treatment without washing off the pretreated cellulose adhering to the inside of the feeding device into the acetylation machine.
酢化終了後、酢酸マグネシウム１５重量％酢酸−水混合溶液を、溶液中の水の
濃度が３．０重量％、硫酸イオン濃度が０．５重量％になるまで添加して無水酢
酸を分解させ、酢化反応を停止し、停止時の水と無水酢酸の反応熱で上昇する温
度で所定時間熟成を行った。その後、常法により精製・乾燥し、フレーク状酢酸
セルロースを得た。 After the completion of the acetylation, a 15 wt % magnesium acetate acetic acid-water mixed solution was added until the water concentration in the solution became 3.0 wt % and the sulfate ion concentration became 0.5 wt % to decompose the acetic anhydride, and the acetylation reaction was terminated. The mixture was then aged for a predetermined time at a temperature increased by the heat of reaction between water and acetic anhydride at the time of terminating the reaction. Thereafter, the mixture was purified and dried by a conventional method to obtain flaky cellulose acetate.
比較例２
セルロースパルプ１００重量部に氷酢酸５０重量部を散布して、前処理活性化
した。この前処理セルロースを酢化機に送綿した後、送綿装置内部に付着してい
る前処理セルロースを酢化機へ洗い落とすことなく、氷酢酸４２０重量部、無水
酢酸２６０重量部、硫酸８重量部を添加し酢化処理を行った。Comparative Example 2: 100 parts by weight of cellulose pulp was pretreated and activated by spraying 50 parts by weight of glacial acetic acid. This pretreated cellulose was fed to an acetylation machine, and then 420 parts by weight of glacial acetic acid, 260 parts by weight of acetic anhydride, and 8 parts by weight of sulfuric acid were added thereto for acetylation without washing off the pretreated cellulose adhering to the inside of the feeding device.
酢化終了後、酢酸マグネシウム１５重量％酢酸−水混合溶液を、溶液中の水の
濃度が３．０重量％、硫酸イオン濃度が０．５重量％になるまで添加して無水酢
酸を分解させ、酢化反応を停止し、系内に過熱蒸気を吹き込み、温度と時間を調
整し熟成を行った。その後、常法により精製・乾燥し、フレーク状酢酸セルロー
スを得た。 After the completion of the acetylation, a 15 wt % magnesium acetate acetic acid-water mixed solution was added until the water concentration in the solution became 3.0 wt % and the sulfate ion concentration became 0.5 wt % to decompose the acetic anhydride, and the acetylation reaction was stopped. Superheated steam was blown into the system and aging was carried out by adjusting the temperature and time. Thereafter, the product was purified and dried by a conventional method to obtain flaky cellulose acetate.
表１に示したように、本発明により、濾過性に優れた酢酸セルロースを製造す
ることができた。 As shown in Table 1, cellulose acetate with excellent filterability could be produced according to the present invention.
───────────────────────────────────────────────────── （注）この公表は、国際事務局（ＷＩＰＯ）により国際公開された公報を基に作 成したものである。 なおこの公表に係る日本語特許出願（日本語実用新案登録出願）の国際公開の 効果は、特許法第１８４条の１０第１項（実用新案法第４８条の１３第２項）に より生ずるものであり、本掲載とは関係ありません。───────────────────────────────────────────────────── (Note) This publication is based on the publication published internationally by the International Bureau of Patents (WIPO). The effect of the international publication of the Japanese patent application (Japanese utility model registration application) related to this publication arises pursuant to Article 184-10, Paragraph 1 of the Patent Act (Article 48-13, Paragraph 2 of the Utility Model Act) and is unrelated to this publication.
Claims (10)
具備することを特徴とする酢酸セルロース，但し（Ｂ）のみを具備する場合を除
く。 要件（Ａ）：２０μｍ以上の輝点異物が２０個／ｍｍ３以下。 （輝点異物の測定方法） 酢酸セルロースをメチレンクロライド／メタノール＝９／１（重量比）混合溶媒
に溶解し、１５重量％（固形分濃度）の溶液（ドープ）を得る。このドープをス
ライドグラス上に流延、乾燥し、スライドグラス上に厚さ１００μｍ程度のフィ
ルム状のサンプルを得る。このサンプルを偏光顕微鏡で暗視野下で観察し、面積
３２ｍｍ２内にある最大長さが２０μｍ以上の輝点異物を数え、別途測定した正
確なフィルムの厚みで補正し、単位体積（１ｍｍ３）あたりの異物数を求める。
異なるドープから製膜したフィルム３枚について同様の測定を行い、それらの平
均値を算出し、輝点異物の数とする。 要件（Ｂ）：閉塞恒数（Ｋ）が６０以下。 （閉塞恒数の測定方法） 酢酸セルロースをメチレンクロライド／メタノール＝９／１（重量比）混合溶媒
に溶解し、１６重量％（固形分濃度）の溶液を得る。この溶液を金巾濾材を使用
して濾過圧力２９４ｋＰａ（３ｋｇ／ｃｍ２）、温度２５℃で定圧濾過し、経時
的に測定した濾過量からｔ／Ｖ〜ｔ［ｔは濾過時間（分）、Ｖは濾過量（ｍｌ）
を示す〕で表される直線の勾配を算出し、Ｋ＝勾配×２×１０４から閉塞恒数（
Ｋ）を求める。 要件（Ｃ）：測定周波数０．０１６Ｈｚの貯蔵弾性率（Ｇ’）と損失弾性率（Ｇ
”）の比（Ｇ’／Ｇ”）が０．２以下。 （動的粘弾性の測定方法） 酢酸セルロース１５．５重量部、トリフェニルホスフェイト１．５重量部及びビ
フェニルジフェニルホスフェイト０．９重量部をメチレンクロライド６９．８重
量部とメタノール１２．３重量部に溶解した溶液を作製する。この溶液の動的粘
弾性（Ｇ’とＧ”）を２５℃で測定する。[Claim 1] Cellulose acetate characterized by satisfying at least one of the following requirements (A), (B), and (C), except when only (B) is satisfied. Requirement (A): The number of bright spots of 20 μm or larger is 20 or less per mm3 . (Method for measuring bright spots) Cellulose acetate is dissolved in a mixed solvent of methylene chloride and methanol at a ratio of 9:1 (by weight) to obtain a 15 wt% (solids concentration) solution (dope). This dope is cast onto a glass slide and dried to obtain a film-like sample on the glass slide with a thickness of approximately 100 μm. This sample is observed under a polarizing microscope under dark field conditions, and bright spots with a maximum length of 20 μm or larger within an area of 32 mm2 are counted. The number of bright spots per unit volume (1 mm3 ) is calculated by correcting for the accurate film thickness measured separately.
The same measurement is carried out for three films made from different dopes, and the average value is calculated and used as the number of bright spot foreign matters. Requirement (B): The blocking constant (K) is 60 or less. (Method of measuring the blocking constant) Cellulose acetate is dissolved in a mixed solvent of methylene chloride/methanol = 9/1 (weight ratio) to obtain a 16 wt% (solid content concentration) solution. This solution is filtered using a gold filter medium at a constant pressure of 294 kPa (3 kg/ cm2 ) and a temperature of 25°C, and t/V~t (t is the filtration time (min), V is the filtration volume (ml)) is calculated from the filtration volume measured over time.
The gradient of the straight line represented by the formula K = gradient × 2 × 104 is calculated, and the occlusion constant (
Requirement (C): The storage modulus (G') and loss modulus (G) at a measurement frequency of 0.016 Hz are calculated.
The ratio (G'/G") of the ratios (G'/G") is 0.2 or less. (Method for measuring dynamic viscoelasticity) A solution is prepared by dissolving 15.5 parts by weight of cellulose acetate, 1.5 parts by weight of triphenyl phosphate, and 0.9 parts by weight of biphenyl diphenyl phosphate in 69.8 parts by weight of methylene chloride and 12.3 parts by weight of methanol. The dynamic viscoelasticity (G' and G") of this solution is measured at 25°C.
）を具備する請求項１に記載した酢酸セルロース。Claim 2: (A) and (B), (A and (C), or (B and (C)
2. The cellulose acetate of claim 1, comprising:
セルロース。4. The cellulose acetate according to claim 1, which satisfies the requirements (A), (B), and (C).
請求項１、２および４のいずれかに記載した酢酸セルロース。5. Cellulose acetate according to any one of claims 1, 2 and 4, wherein the number of bright foreign particles of 20 μm or more as specified in requirement (A) is 10/ mm³ or less.
した酢酸セルロース。6. The cellulose acetate according to claim 3 or 4, wherein the G'/G" of requirement (C) is 0.1 or less.
載した酢酸セルロース。7. The cellulose acetate according to claim 3 or 4, wherein the G'/G" of requirement (C) is 0.06 or less.
反応系に送る送綿工程及び酢化反応工程を含む酢酸セルロースの製造方法におい
て、送綿工程の送綿経路に付着した前処理セルロースを、酢化反応開始に先立ち
酢酸又は酢酸と無水酢酸混合液で酢化反応系内へ洗い落とすことを特徴とする請
求項１に記載した酢酸セルロースの製造方法。[Claim 8] A method for producing cellulose acetate comprising a pretreatment step of treating cellulose with acetic acid, a cotton-feeding step of sending the pretreated cellulose to an acetylation reaction system, and an acetylation reaction step, characterized in that the pretreated cellulose adhering to the cotton-feeding path in the cotton-feeding step is washed off into the acetylation reaction system with acetic acid or a mixture of acetic acid and acetic anhydride prior to the start of the acetylation reaction.
ロース１００重量部に対し５〜５０容量部である請求項８に記載した方法。9. The method according to claim 8, wherein the amount of acetic acid or the mixture of acetic acid and acetic anhydride used for washing is 5 to 50 parts by volume per 100 parts by weight of the starting cellulose.
した方法。10. The method according to claim 8 or 9, wherein the cellulose acetate is cellulose triacetate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000-86998 | 2000-03-27 | ||
| JP2000086998 | 2000-03-27 | ||
| PCT/JP2001/002478 WO2001072847A1 (en) | 2000-03-27 | 2001-03-27 | Cellulose acetate and process for producing the same |
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| JP2010033573A Division JP5171859B2 (en) | 2000-03-27 | 2010-02-18 | Cellulose acetate and method for producing the same |
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| JPWO2001072847A1 true JPWO2001072847A1 (en) | 2003-07-08 |
| JP4509454B2 JP4509454B2 (en) | 2010-07-21 |
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| JP2001571778A Expired - Lifetime JP4509454B2 (en) | 2000-03-27 | 2001-03-27 | Cellulose acetate and method for producing the same |
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|---|---|
| US (1) | US6803458B2 (en) |
| EP (1) | EP1270597B1 (en) |
| JP (2) | JP4509454B2 (en) |
| KR (1) | KR100694285B1 (en) |
| CN (1) | CN1243023C (en) |
| TW (1) | TW539678B (en) |
| WO (1) | WO2001072847A1 (en) |
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| JP4786909B2 (en) * | 2005-02-01 | 2011-10-05 | ダイセル化学工業株式会社 | Cellulose mixed acid ester and method for producing the same |
| JP5073248B2 (en) * | 2006-08-30 | 2012-11-14 | 株式会社ダイセル | Cellulose acetate and method for producing the same |
| US20100175691A1 (en) * | 2009-01-15 | 2010-07-15 | Celanese Acetate Llc | Process for recycling cellulose acetate ester waste |
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| US10383369B2 (en) | 2017-06-07 | 2019-08-20 | Rai Strategic Holdings, Inc. | Fibrous filtration material for electronic smoking article |
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| WO2022195803A1 (en) * | 2021-03-18 | 2022-09-22 | 株式会社ダイセル | Cellulose acetate and method for producing same |
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-
2001
- 2001-03-26 TW TW090107063A patent/TW539678B/en not_active IP Right Cessation
- 2001-03-27 CN CNB018071848A patent/CN1243023C/en not_active Expired - Lifetime
- 2001-03-27 EP EP01915837.7A patent/EP1270597B1/en not_active Expired - Lifetime
- 2001-03-27 WO PCT/JP2001/002478 patent/WO2001072847A1/en not_active Ceased
- 2001-03-27 JP JP2001571778A patent/JP4509454B2/en not_active Expired - Lifetime
- 2001-03-27 KR KR1020027012773A patent/KR100694285B1/en not_active Expired - Fee Related
- 2001-03-27 US US10/239,628 patent/US6803458B2/en not_active Expired - Lifetime
-
2010
- 2010-02-18 JP JP2010033573A patent/JP5171859B2/en not_active Expired - Fee Related
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