JPH0931880A - Bleaching and modification of chemical pulp - Google Patents
Bleaching and modification of chemical pulpInfo
- Publication number
- JPH0931880A JPH0931880A JP18014395A JP18014395A JPH0931880A JP H0931880 A JPH0931880 A JP H0931880A JP 18014395 A JP18014395 A JP 18014395A JP 18014395 A JP18014395 A JP 18014395A JP H0931880 A JPH0931880 A JP H0931880A
- Authority
- JP
- Japan
- Prior art keywords
- bleaching
- pulp
- chelating agent
- enzyme
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、化学パルプの漂白
法及び改質法に関する。更に詳しくは、化学パルプの漂
白と改質において、バチルスｓｐ．ＳＤ９０２株由来の
酵素（以下ＳＤ酵素という）とキレート剤の同時処理、
又は界面活性剤とキレート剤と該酵素による同時前処理
によって、脱リグニンとセルロースの改質を同時に行う
ことを特徴とする化学パルプの漂白法及び改質法であ
る。TECHNICAL FIELD The present invention relates to a bleaching method and a reforming method for chemical pulp. More specifically, in bleaching and modifying chemical pulp, Bacillus sp. Simultaneous treatment of SD902 strain-derived enzyme (hereinafter referred to as SD enzyme) and a chelating agent,
Alternatively, it is a method for bleaching and modifying a chemical pulp, characterized in that delignification and modification of cellulose are carried out simultaneously by simultaneous pretreatment with a surfactant, a chelating agent and the enzyme.
【０００２】[0002]
【従来の技術】化学パルプ漂白の目的は、パルプ繊維の
内部や表面に付着しているリグニンや着色物質を分解、
変質、或は可溶性にして取り除き、白色度を上昇させる
ことである。BACKGROUND OF THE INVENTION The purpose of chemical pulp bleaching is to decompose lignin and coloring substances adhering to the inside and surface of pulp fibers,
Altering or solubilizing it to remove it to increase whiteness.
【０００３】従来、化学パルプの漂白は、塩素、二酸化
塩素、次亜塩素酸塩、過酸化水素、等で段階的に処理す
る方法が採られてきた。近年は、排水負荷量の軽減及び
漂白薬品費の削減を目的として酸素漂白方法が多く採用
されている。Conventionally, the bleaching of chemical pulp has been carried out by a stepwise treatment with chlorine, chlorine dioxide, hypochlorite, hydrogen peroxide and the like. In recent years, an oxygen bleaching method has been widely adopted for the purpose of reducing the load of waste water and reducing the cost of bleaching chemicals.
【０００４】一方、最近は、ダイオキシンを含む、ＡＯ
Ｘ（吸着性有機ハロゲン化合物）の規制や安全性の点か
ら、塩素系薬品を使用しない、いわゆる非塩素漂白方法
が開発され実施されるようになってきた。非塩素漂白方
法には、塩素及び二酸化塩素等の塩素系薬品を全く使用
しないＴＣＦ方法、塩素のみを使用しないＥＣＦ方法が
ある。On the other hand, recently, AO containing dioxin
From the standpoint of regulation of X (adsorbable organic halogen compound) and safety, so-called non-chlorine bleaching method, which does not use chlorine-based chemicals, has been developed and implemented. Non-chlorine bleaching methods include a TCF method that does not use chlorine and chlorine dioxide and other chlorine-based chemicals at all, and an ECF method that does not use chlorine alone.
【０００５】非塩素漂白方法の一つである過酸化物及び
オゾンによる漂白方法は、既に公知である。過酸化物又
はオゾン漂白ではパルプが前処理されていない限り、過
酸化物又はオゾンがパルプスラリー中に存在するＭｎ、
Ｆｅ等の微量金属によって分解され、漂白効率が低下す
る。そのために漂白剤を多量に使用することとなり、コ
ストアップにつながる。且つ分解によって生じたラジカ
ル等の化学種によるパルプ粘度及び収率の低下等の問題
がある。A bleaching method using peroxide and ozone, which is one of the chlorine-free bleaching methods, is already known. In peroxide or ozone bleaching, Mn, where peroxide or ozone is present in the pulp slurry, unless the pulp has been pretreated.
It is decomposed by trace metals such as Fe and the bleaching efficiency decreases. Therefore, a large amount of bleach is used, which leads to an increase in cost. In addition, there are problems such as reduction in pulp viscosity and yield due to chemical species such as radicals generated by decomposition.
【０００６】そこで、微量金属の対策として、特開平５
−１４８７８４号公報では、リグノセルロース含有パル
プをｐＨ１〜６の範囲で酸処理した後、アルカリ土類金
属含有化合物をｐＨ１〜７の範囲で処理するオゾン、過
酸化物の漂白方法が開示されている。又、特開平５−１
４８７８５号公報では、リグノセルロース含有パルプを
ｐＨ３．１〜９．０の範囲内で、窒素ポリカルボン酸の
錯化剤により処理するオゾン、過酸化物の漂白方法が開
示されている。Therefore, as a countermeasure against trace metals, Japanese Patent Application Laid-Open
JP-A-148784 discloses a method for bleaching ozone and peroxide in which lignocellulose-containing pulp is acid-treated in the range of pH 1 to 6 and then alkaline earth metal-containing compound is treated in the range of pH 1 to 7. . Also, Japanese Patent Laid-Open No. 5-1
Japanese Patent No. 48785 discloses a method for bleaching ozone and peroxide in which lignocellulose-containing pulp is treated with a complexing agent of nitrogen polycarboxylic acid within a pH range of 3.1 to 9.0.
【０００７】一方、最近、酵素によるパルプの処理方法
も研究されている。酵素としては、セルラーゼ、キシラ
ナーゼ、ペクチナーゼ、リパーゼ等が知られている。例
えば、特開平２−２６４０８７号公報では、ｐＨ４〜８
のキシラナーゼを含む酵素による未晒パルプの処理方
法、又、特開平２−２９３４８６号公報では、ｐＨ３〜
１０でヘミセルラーゼを含む酵素による未晒パルプの処
理方法等が提案されている。一般に非塩素漂白を行う場
合、これらの前処理が極めて有効である。On the other hand, recently, a method for treating pulp with an enzyme has been studied. Known enzymes are cellulase, xylanase, pectinase, lipase and the like. For example, in JP-A-2-264087, pH 4-8
Of unbleached pulp with an enzyme containing xylanase described in JP-A-2-293486, pH 3 to
In 10, a method for treating unbleached pulp with an enzyme containing hemicellulase has been proposed. In general, these pretreatments are extremely effective when performing non-chlorine bleaching.
【０００８】更に、酵素によるパルプの改質方法が研究
されている。例えば、特開平２−２０７５６号公報で
は、抄紙時にセルラーゼとセロビオースを１／０．０５
〜０．５の比率で添加することで叩解性を改善させ叩解
電力を低減させる方法が提案されている。又、特公昭６
３−１３５５９７号公報では、ＦＰ活性が２０ｍｇ／酵
素ｇ以上の酵素を添加することでベッセルピックを防止
する方法が提案されている。しかし、これらの方法は、
非塩素漂白の前処理効果とセルロースの改質を同時に与
えることができないという問題があった。[0008] Further, enzymatic pulp modification methods have been investigated. For example, in Japanese Patent Application Laid-Open No. 2-20756, cellulase and cellobiose are added at 1 / 0.05 at the time of paper making.
A method has been proposed in which the beating property is improved and the beating power is reduced by adding it at a ratio of 0.5. Also, Tokubiko 6
JP-A-3-135597 proposes a method of preventing a Bessel pick by adding an enzyme having an FP activity of 20 mg / g enzyme or more. However, these methods
There is a problem that the pretreatment effect of non-chlorine bleaching and the modification of cellulose cannot be provided at the same time.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、前記
問題点を解決して、非塩素漂白の前処理とセルロースの
改質を同時に行い、叩解性が改善されてベッセルピック
が発生しない非塩素漂白パルプを提供することである。SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems and to perform pretreatment of non-chlorine bleaching and modification of cellulose at the same time to improve beating property and prevent vessel picking. Providing chlorine bleached pulp.
【００１０】[0010]
【課題を解決するための手段】本発明者等は、上記の問
題点を解決すべく鋭意研究を重ねた結果、蒸解あるいは
酸素漂白後の化学パルプにＳＤ酵素とキレート剤による
同時処理、又は界面活性剤とキレート剤とＳＤ酵素の同
時前処理によって、脱リグニンによる漂白性の改善とセ
ルロースの改質を同時に行える効果があることを見い出
しこの知見に基づき本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that chemical pulp after digestion or oxygen bleaching is simultaneously treated with SD enzyme and a chelating agent, or at the interface. It has been found that simultaneous pretreatment of an activator, a chelating agent and SD enzyme has the effect of simultaneously improving bleaching property by delignification and modifying cellulose, and based on this finding, the present invention has been completed.
【００１１】従って、本発明は、酵素とキレート剤の相
乗効果又は酵素とキレート剤、界面活性剤の相乗効果に
より前記の問題点を解決し、化学パルプの漂白性が向上
することで、易叩解、高白色度、高収率の非塩素漂白パ
ルプが得られ、且つ叩解時に繊維がフィブリル化され易
くなり、ベッセルピックや紙ムケの防止が可能である化
学パルプの漂白法及び改質法である。Therefore, the present invention solves the above-mentioned problems by the synergistic effect of the enzyme and the chelating agent or the synergistic effect of the enzyme, the chelating agent and the surfactant, and improves the bleaching property of the chemical pulp. A high-whiteness, high-yield non-chlorine bleached pulp is obtained, and fibers are easily fibrillated during beating, which is a bleaching method and a reforming method for chemical pulp, which can prevent vessel picking and waste of paper. .
【００１２】即ち、本発明は、蒸解あるいは酸素漂白後
の化学パルプにバチルスｓｐ、ＳＤ９０２株由来の酵素
とキレート剤とで同時に処理するか、又はＳＤ９０２株
由来の酵素とキレート剤と界面活性剤とで同時に処理
し、その後で漂白し、叩解する化学パルプの漂白方法及
び改質方法である。That is, according to the present invention, chemical pulp after cooking or oxygen bleaching is simultaneously treated with an enzyme derived from Bacillus sp. SD902 strain and a chelating agent, or an enzyme derived from SD902 strain, a chelating agent and a surfactant is added. Is a method for bleaching and modifying a chemical pulp in which the pulp is treated at the same time and then bleached and beaten.
【００１３】該酵素による処理条件は、処理ｐＨ３〜
９、処理温度２０〜９０℃、処理時間１５〜１８０分、
パルプ濃度は２〜１５重量％で、酵素の添加量はキシラ
ナーゼ活性として０．１〜１０００Ｕ／ｇ（対絶乾パル
プ）である。キレート剤を添加する場合は添加量は０．
０１〜５重量％（対絶乾パルプ）であり、キレート剤と
界面活性剤とを添加する場合は、添加量は両者共０．０
１〜５重量％（対絶乾パルプ）である。The treatment conditions with the enzyme are treatment pH 3 to
9, processing temperature 20 ~ 90 ℃, processing time 15 ~ 180 minutes,
The pulp concentration is 2 to 15% by weight, and the amount of enzyme added is 0.1 to 1000 U / g (versus dry pulp) as xylanase activity. When a chelating agent is added, the addition amount is 0.
01 to 5% by weight (vs. absolute dry pulp), and when a chelating agent and a surfactant are added, the addition amount of both is 0.0
1 to 5% by weight (vs. absolute dry pulp).
【００１４】前記キレート剤としては、窒素を含む有機
キレート剤及び高分子の塩のキレート剤よりなる群より
選んだ少なくとも一種を使用し、前記界面活性剤として
は、ノニオン性、カチオン性、アニオン性、両性の有機
界面活性剤及び高分子界面活性剤よりなる群より選んだ
少なくとも一種を使用する。At least one selected from the group consisting of nitrogen-containing organic chelating agents and polymeric salt chelating agents is used as the chelating agent, and the surfactant is nonionic, cationic, or anionic. At least one selected from the group consisting of amphoteric organic surfactants and polymer surfactants is used.
【００１５】前記のキレート剤と該酵素との同時処理、
又は界面活性剤とキレート剤と、該酵素との同時処理の
白水を向流的に前の処理段に戻し、最終的に黒液回収工
程に送ることが、これらの薬剤を十分に活用することに
なり好ましい。Simultaneous treatment of the above chelating agent and the enzyme,
Alternatively, it is possible to return the white water of the simultaneous treatment of the surfactant, the chelating agent and the enzyme to the previous treatment stage countercurrently and finally send it to the black liquor recovery step in order to fully utilize these agents. And is preferable.
【００１６】前記酵素とキレート剤との同時処理又は前
記酵素とキレート剤と界面活性剤との同時処理の後の漂
白方法としては、オゾン、過酸化物、過酸化物と酸素、
二酸化チオ尿素よりなる群より選んだ少なくとも一種に
より漂白するか、又この漂白では塩素化合物量としては
僅かでよいので前記群に二酸化塩素、次亜塩素酸塩を加
えた群より選んだ少なくとも一種によって漂白するもの
である。As the bleaching method after the simultaneous treatment of the enzyme and the chelating agent or the simultaneous treatment of the enzyme, the chelating agent and the surfactant, ozone, peroxide, peroxide and oxygen,
Bleach with at least one selected from the group consisting of thiourea dioxide, or at least one selected from the group containing chlorine dioxide and hypochlorite in the above group because the amount of chlorine compound in this bleaching may be small. It is bleaching.
【００１７】[0017]
【発明の実施の形態】本発明に使用できる酵素は、ＳＤ
酵素である。ＳＤ酵素は受託番号ＦＥＲＭＰ−１３３５
６として工業技術院生命工学工業技術研究所に寄託さ
れ、その後国際寄託に移管されて受託番号ＦＥＲＭ Ｂ
Ｐ−４５０８が付与されている。この菌株を特開平６−
２６１７５０号公報に記載の方法に従って培養し、酵素
を調製することができる。BEST MODE FOR CARRYING OUT THE INVENTION The enzyme usable in the present invention is SD
It is an enzyme. SD enzyme is accession number FERMP-1335
6 was deposited at the Institute of Biotechnology, Institute of Biotechnology, and then transferred to an international deposit, and the deposit number was FERM B.
P-4508 is assigned. This strain was designated as JP-A-6-
The enzyme can be prepared by culturing according to the method described in Japanese Patent No. 261750.
【００１８】本発明に使用されるキレート剤は、窒素を
含む有機の塩からなるキレート剤、又は高分子の塩から
なるキレート剤である。例えば、エチレンジアミン４酢
酸ナトリウム（ＥＤＴＡ−４Ｎａ）、ジエチレントリア
ミン５酢酸ナトリウム（ＤＴＰＡ−５Ｎａ）等の有機の
塩からなるキレート剤、更にポリアルキレンポリアミン
ポリアセテートのような高分子の塩からなるキレート剤
等を挙げることができる。尚、塩としては、Ｋ、Ｃａ、
Ｍｇ等が挙げられる。更に、これらのキレート剤２種類
以上を併用することもできる。The chelating agent used in the present invention is a chelating agent composed of an organic salt containing nitrogen or a chelating agent composed of a polymer salt. For example, a chelating agent composed of an organic salt such as ethylenediaminetetraacetic acid sodium salt (EDTA-4Na) and sodium diethylenetriaminepentaacetate (DTPA-5Na), a chelating agent composed of a polymer salt such as polyalkylenepolyaminepolyacetate, and the like may be used. Can be mentioned. Incidentally, as the salt, K, Ca,
Mg etc. are mentioned. Furthermore, two or more kinds of these chelating agents can be used in combination.
【００１９】本発明に使用される界面活性剤は、両性、
ノニオン性、カチオン性、アニオン性で有機又は高分子
の界面活性剤である。例えば、両性としては、Ｎ−アル
キルベタイン、Ｎーアルキルスルホタイン等；ノニオン
性としては、ポリオキシエチレンアルキルエーテル、ポ
リオキシエチレンソルビタンアルキルエステル等；カチ
オン性としては、ポリアクリルアミド、アルキルアンモ
ニウムブロマイド等；アニオン性としては、ポリアクリ
ル酸塩、ポリカルボン酸塩等；が挙げられる。更に、こ
れらの界面活性剤２種類以上を併用することもできる。Surfactants used in the present invention are amphoteric,
It is a nonionic, cationic, anionic, organic or polymeric surfactant. For example, N-alkylbetaine, N-alkylsulfotaine and the like as amphoteric; polyoxyethylene alkyl ether, polyoxyethylene sorbitan alkyl ester and the like as nonionic; polyacrylamide, alkylammonium bromide and the like as cationic; Examples of the anionic property include polyacrylic acid salts and polycarboxylic acid salts. Further, two or more kinds of these surfactants can be used together.
【００２０】本発明が適用される化学パルプは、蒸解あ
るいは酸素漂白された針葉樹又は広葉樹パルプである。The chemical pulp to which the present invention is applied is a cooked or oxygen-bleached softwood or hardwood pulp.
【００２１】本発明の酵素とキレート剤、界面活性剤を
用いた処理の条件は、以下のとおりである。The conditions of the treatment using the enzyme of the present invention, the chelating agent and the surfactant are as follows.
【００２２】酵素の添加量は、キシラナーゼ活性とし
て、０．１〜１０００Ｕ／ｇ、好ましくは１〜５００Ｕ
／ｇである。ここで、酵素の添加量が０．１Ｕ／ｇ未満
では処理効果がなく、１０００Ｕ／ｇを超える場合は、
収率、粘度の低下が激しい。The amount of enzyme added is 0.1 to 1000 U / g, preferably 1 to 500 U, as xylanase activity.
/ G. Here, when the amount of enzyme added is less than 0.1 U / g, there is no treatment effect, and when it exceeds 1000 U / g,
Yield and viscosity decrease drastically.
【００２３】キレート剤又はキレート剤と界面活性剤を
添加する場合は、キレート剤と界面活性剤の添加量はと
もに、０．０１〜５重量％、好ましくは０．０５〜３重
量％である。ここで、キレート剤及び界面活性剤の添加
量が０．０１重量％未満では処理効果がほとんどなく、
５重量％を超える場合は効果が飽和し、量に応じた効果
が十分でなく経済的にも不利である。When the chelating agent or the chelating agent and the surfactant are added, the addition amount of both the chelating agent and the surfactant is 0.01 to 5% by weight, preferably 0.05 to 3% by weight. Here, if the addition amount of the chelating agent and the surfactant is less than 0.01% by weight, there is almost no treatment effect,
If it exceeds 5% by weight, the effect is saturated, the effect depending on the amount is not sufficient, and it is economically disadvantageous.
【００２４】パルプ濃度は、２〜１５重量％、好ましく
は３〜１２重量％である。ここで、パルプ濃度が２重量
％未満では処理効率が悪く、１５重量％より濃い場合に
は、攪拌混合が不十分となり好ましくない。The pulp concentration is 2 to 15% by weight, preferably 3 to 12% by weight. Here, when the pulp concentration is less than 2% by weight, the treatment efficiency is poor, and when the pulp concentration is more than 15% by weight, stirring and mixing are insufficient, which is not preferable.
【００２５】パルプ処理温度は、２０〜９０℃、好まし
くは４０〜７０℃である。ここで、処理温度が２０℃未
満では処理効率が遅く、９０℃を超える場合は酵素の効
果が現れない。The pulp treatment temperature is 20 to 90 ° C, preferably 40 to 70 ° C. Here, if the treatment temperature is lower than 20 ° C, the treatment efficiency is slow, and if it exceeds 90 ° C, the effect of the enzyme does not appear.
【００２６】パルプ処理時間は、１５〜１８０分、好ま
しくは３０〜１２０分である。ここで、処理時間が１５
分未満では効果が小さく、１８０分より長くしてもそれ
以上の効果が現れない。The pulp treatment time is 15 to 180 minutes, preferably 30 to 120 minutes. Here, the processing time is 15
If it is less than a minute, the effect is small, and if it is longer than 180 minutes, no further effect appears.
【００２７】パルプ処理ｐＨは、３〜９、好ましくは４
〜８である。ここで、処理ｐＨが３未満又は９より高い
場合、酵素の効果が現れない。尚、処理ｐＨが７〜９の
弱アルカリ側にて収率並びに粘度の低下が防止できる。Pulp treatment pH is 3-9, preferably 4.
~ 8. Here, when the treatment pH is less than 3 or higher than 9, the effect of the enzyme does not appear. It is possible to prevent a decrease in yield and viscosity on the weak alkaline side where the treatment pH is 7 to 9.
【００２８】キシラナーゼ活性は、各酵素の至適ｐＨ、
５０℃の反応条件で生成した還元糖量を公知の方法であ
る３，５−ジニトロサリチル酸法にて測定する。この条
件で、１分間に１μｍｏｌのキシロースを遊離する酵素
量を１Ｕとする。The xylanase activity is the optimum pH of each enzyme,
The amount of reducing sugar produced under the reaction condition of 50 ° C. is measured by a known method of 3,5-dinitrosalicylic acid method. Under this condition, the amount of enzyme that releases 1 μmol of xylose per minute is 1 U.
【００２９】キレート剤と酵素同時処理、又は界面活性
剤とキレート剤と酵素同時処理の白水を向流的に前の処
理段に戻し、最終的に黒液回収工程に送ることができ
る。The white water treated with the chelating agent and the enzyme at the same time, or the surfactant, the chelating agent and the enzyme treated with each other can be countercurrently returned to the previous treatment stage and finally sent to the black liquor recovery step.
【００３０】化学パルプの酵素処理後の漂白方法とし
て、二酸化塩素、次亜塩素酸塩、オゾン、過酸化物又は
過酸化物と酸素、二酸化チオ尿素のいずれか又は複数の
組み合わせにて漂白することができる。As a bleaching method after enzymatic treatment of chemical pulp, bleaching is carried out with chlorine dioxide, hypochlorite, ozone, peroxide or one or a combination of peroxide and oxygen, thiourea dioxide. You can
【００３１】本発明の化学パルプの漂白法及び改質法
は、蒸解あるいは酸素漂白後の化学パルプにＳＤ酵素と
キレート剤による同時処理、又は界面活性剤とキレート
剤と酵素の同時前処理によって、脱リグニンによる漂白
性の改善とセルロースの改質を同時に行える効果があ
る。その結果、易叩解、高白色度、高収率の非塩素漂白
パルプが得られ、且つ叩解時に繊維がフィブリル化され
易くなり、ベッセルピックや紙ムケの防止が可能であ
る。更に、漂白薬品の添加量が少なくて済むだけでな
く、漂白排水のＡＯＸ、ＣＯＤ、色度の低減効果が見ら
れる。The chemical pulp bleaching method and reforming method of the present invention are carried out by simultaneously treating the chemical pulp after cooking or oxygen bleaching with SD enzyme and a chelating agent, or by simultaneously pretreating a surfactant, a chelating agent and an enzyme. It has the effect of improving the bleaching property by delignification and simultaneously modifying the cellulose. As a result, easily beaten, high whiteness and high yield non-chlorine bleached pulp can be obtained, and the fibers are easily fibrillated during beating, and it is possible to prevent vessel picking and waste of paper. Furthermore, not only the amount of bleaching chemicals added is small, but the effects of reducing AOX, COD, and chromaticity of bleaching wastewater can be seen.
【００３２】[0032]
【実施例】以下に実施例を挙げて本発明を具体的に説明
するが、本発明は本実施例に限定されるものではない。
尚、実施例において記載の部、％は全て重量部、重量％
によるものである。又、白色度は、ＪＩＳ−Ｐ８１２
３、パルプ粘度は、ＴＡＰＰＩ Ｔ−２３０ ｏｍー８
２、カッパー価は、ＴＡＰＰＩ Ｔ−２３６ ｈｍ−８
５、濾水度は、ＪＩＳ−Ｐ８１２１、不透明度は、ＪＩ
Ｓ−Ｐ８１３８、引張強度は、ＪＩＳ−Ｐ８１１３、引
裂強度は、ＪＩＳ−Ｐ８１１９、平滑度は、ＴＡＰＰＩ
Ｔ−４７９、内部結合は、インターナルボンドテスタ
（東洋精機製作所社製）、ベッセルピックは、ＲＩ試験
機（明製作所社製）にて１０ｃｍ2あたりのベッセル
数、ＣＯＤ、色度はＪＩＳ−Ｋ０１０２、ＡＯＸは全有
機ハロゲン分析装置ＴＯＸー１０型（三菱化成社製）に
て測定した。その結果は表１、２に示す。The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
All parts and percentages described in the examples are parts by weight and% by weight.
It is due to. The whiteness is measured according to JIS-P812.
3. The pulp viscosity is TAPPI T-230 om-8
2. Copper value is TAPPI T-236 hm-8
5. Freeness is JIS-P8121, opacity is JI
S-P8138, tensile strength: JIS-P8113, tear strength: JIS-P8119, smoothness: TAPPI
T-479, internal bond is internal bond tester (manufactured by Toyo Seiki Seisakusho), and vessel pick is RI tester (manufactured by Mei Seisakusho), and the number of vessels per 10 cm 2 , COD, and chromaticity are JIS-K0102. , AOX were measured with an all-organic halogen analyzer TOX-10 (manufactured by Mitsubishi Kasei). The results are shown in Tables 1 and 2.
【００３３】（実施例１）広葉樹（ユーカリ系約７０％
配合）の酸素漂白パルプ（カッパー価９．５、粘度２
３．５ｃｐ、白色度４４．７％）に、酵素はＳＤ酵素
（昭和電工社製）をキシラナーゼ活性として２０Ｕ／ｇ
（対絶乾パルプ）とキレート剤はアボスＥ−３９０（日
東化学社製、ＤＴＰＡ−Ｎａ）０．２％（対絶乾パル
プ）を同時に添加混合し、パルプ濃度３．５％に調製
し、ｐＨ６．５、６０℃で１時間反応させた。その後、
洗浄脱水し、Ｐ／Ｅ（過酸化水素／水酸化ナトリウム）
−Ｈ／Ｅ（次亜塩素酸ソーダ／水酸化ナトリウム）−Ｄ
（二酸化塩素）にて漂白し、更にＰＦＩミルにて叩解
（以下全て３０００ｒｐｍ）し、坪量６０ｇ／ｍ2の手
すき紙を作成した。尚、Ｐの添加率は１．０％、Ｅの添
加率は０．５％で、反応温度は８０℃、反応時間は２時
間漂白した。Ｈの添加率は０．８％、Ｅの添加率は０．
２％で、反応温度は６５℃、反応時間は２．５時間漂白
した。Ｄの添加率は０．２５％で、反応温度は７５℃、
反応時間は３時間漂白した。各漂白におけるパルプ濃度
は全て１２％にて行った。(Example 1) Broad-leaved tree (eucalyptus-based about 70%
Blended oxygen bleached pulp (Kappa number 9.5, viscosity 2)
The enzyme has SD enzyme (manufactured by Showa Denko KK) as xylanase activity of 20 U / g at 3.5 cp and whiteness of 44.7%.
(Anti-dry pulp) and a chelating agent were added and mixed with Avos E-390 (manufactured by Nitto Chemical Co., DTPA-Na) 0.2% (an absolute dry pulp) at the same time to prepare a pulp concentration of 3.5%. The reaction was carried out at pH 6.5 and 60 ° C. for 1 hour. afterwards,
Washed and dehydrated, P / E (hydrogen peroxide / sodium hydroxide)
-H / E (sodium hypochlorite / sodium hydroxide) -D
It was bleached with (chlorine dioxide) and beaten with a PFI mill (hereinafter, all 3000 rpm) to prepare a handsheet with a basis weight of 60 g / m 2 . The P addition rate was 1.0%, the E addition rate was 0.5%, the reaction temperature was 80 ° C., and the reaction time was bleaching for 2 hours. The H addition rate was 0.8%, and the E addition rate was 0.
At 2%, the reaction temperature was 65 ° C. and the reaction time was 2.5 hours. The addition rate of D is 0.25%, the reaction temperature is 75 ° C,
The reaction time was bleaching for 3 hours. The pulp concentration in each bleaching was all 12%.
【００３４】（実施例２）実施例１と同様のパルプに、
ＳＤ酵素をキシラナーゼ活性として２Ｕ／ｇとアボスＥ
−３９０を０．２％を同時に添加混合し、パルプ濃度
３．５％に調製し、ｐＨ６、６０℃で１時間反応させ
た。その後、洗浄脱水し、Ｐ／Ｅ−Ｈ／Ｅ−Ｄにて漂白
し、更にＰＦＩミルにて叩解し、坪量６０ｇ／ｍ2の手
すき紙を作成した。尚、Ｐの添加率は１．０％、Ｅの添
加率は０．５％で、反応温度は８０℃、反応時間は２時
間漂白した。Ｈの添加率は０．８％、Ｅの添加率は０．
２％で、反応温度は６５℃、反応時間は２．５時間漂白
した。Ｄの添加率は０．２５％で、反応温度は７５℃、
反応時間は３時間漂白した。実施例１と同様のパルプ濃
度で行った。Example 2 The same pulp as in Example 1 was used,
SD enzyme with xylanase activity of 2 U / g and Avos E
0.2% of -390 was simultaneously added and mixed to prepare a pulp concentration of 3.5%, and the mixture was reacted at pH 6 and 60 ° C. for 1 hour. Then, it was washed and dehydrated, bleached with P / E-H / E-D, and further beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 . The P addition rate was 1.0%, the E addition rate was 0.5%, the reaction temperature was 80 ° C., and the reaction time was bleaching for 2 hours. The H addition rate was 0.8%, and the E addition rate was 0.
At 2%, the reaction temperature was 65 ° C. and the reaction time was 2.5 hours. The addition rate of D is 0.25%, the reaction temperature is 75 ° C,
The reaction time was bleaching for 3 hours. The same pulp concentration as in Example 1 was used.
【００３５】（実施例３）実施例１と同様のパルプに、
ＳＤ酵素をキシラナーゼ活性として２０Ｕ／ｇとキレー
ト剤としてネオクリスタル８０（日華化学社製、ポリア
ルキレンポリアミンポリアセテートＮａ）を０．２％を
同時に添加混合し、パルプ濃度３．５％に調製し、ｐＨ
６、６０℃で１時間反応させた。その後、洗浄脱水し、
Ｐ／Ｅ−Ｈ／Ｅ−Ｄにて漂白し、更にＰＦＩミルにて叩
解し、坪量６０ｇ／ｍ2の手すき紙を作成した。尚、Ｐ
の添加率は１．０％、Ｅの添加率は０．５％で、反応温
度は８０℃、反応時間は２時間漂白した。Ｈの添加率は
０．８％、Ｅの添加率は０．２％で、反応温度は６５
℃、反応時間は２．５時間漂白した。Ｄの添加率は０．
２５％で、反応温度は７５℃、反応時間は３時間漂白し
た。実施例１と同様のパルプ濃度で行った。Example 3 The same pulp as in Example 1 was used.
20 U / g of SD enzyme as xylanase activity and 0.2% of NeoCrystal 80 (polyalkylene polyamine polyacetate Na, manufactured by Nichika Chemical Co., Ltd.) as chelating agent were simultaneously added and mixed to prepare a pulp concentration of 3.5%. , PH
6, reacted at 60 ° C. for 1 hour. After that, wash and dehydrate,
It was bleached with P / E-H / E-D and beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 . Note that P
The bleaching rate was 1.0%, the addition rate of E was 0.5%, the reaction temperature was 80 ° C., and the reaction time was 2 hours. The addition rate of H was 0.8%, the addition rate of E was 0.2%, and the reaction temperature was 65%.
Bleaching was carried out for 2.5 hours at ℃. The addition rate of D is 0.
At 25%, the reaction temperature was 75 ° C., and the reaction time was 3 hours. The same pulp concentration as in Example 1 was used.
【００３６】（実施例４）実施例１と同様のパルプに、
ＳＤ酵素をキシラナーゼ活性として２０Ｕ／ｇとアボス
Ｅ−３９０を０．１％、界面活性剤はプライマール８５
０（プライマール社製、アニオン界面活性剤）０．１％
を同時に添加混合し、パルプ濃度３．５％に調製し、ｐ
Ｈ６．５、６０℃で１時間反応させた。その後、洗浄脱
水し、Ｐ／Ｅ−Ｈ／Ｅ−Ｄにて漂白し、更にＰＦＩミル
にて叩解し、坪量６０ｇ／ｍ2の手すき紙を作成した。
尚、Ｐの添加率は１．０％、Ｅの添加率は０．５％で、
反応温度は８０℃、反応時間は２時間漂白した。Ｈの添
加率は０．８％、Ｅの添加率は０．２％で、反応温度は
６５℃、反応時間は２．５時間漂白した。Ｄの添加率は
０．２５％で、反応温度は７５℃、反応時間は３時間漂
白した。実施例１と同様のパルプ濃度で行った。(Example 4) The same pulp as in Example 1 was used.
20 U / g of SD enzyme as xylanase activity and 0.1% of Avos E-390, and surfactant of Primal 85
0 (Primal Co., anionic surfactant) 0.1%
Are added and mixed at the same time to prepare a pulp concentration of 3.5%, and p
The reaction was carried out at H6.5 and 60 ° C. for 1 hour. Then, it was washed and dehydrated, bleached with P / E-H / E-D, and further beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 .
The P addition rate was 1.0% and the E addition rate was 0.5%.
The reaction temperature was 80 ° C., and the reaction time was bleaching for 2 hours. The H content was 0.8%, the E content was 0.2%, the reaction temperature was 65 ° C., and the reaction time was 2.5 hours. The addition rate of D was 0.25%, the reaction temperature was 75 ° C., and the reaction time was bleaching for 3 hours. The same pulp concentration as in Example 1 was used.
【００３７】（実施例５）実施例１と同様のパルプに、
ＳＤ酵素をキシラナーゼ活性として２０Ｕ／ｇ、アボス
Ｅ−３９０を０．１％、界面活性剤はＮＳ２０６（日産
化学社製、ノニオン界面活性剤）０．１％を同時に添加
混合し、パルプ濃度３．５％に調製し、ｐＨ６．５、６
０℃で１時間反応させた。その後、洗浄脱水し、Ｐ／Ｅ
−Ｈ／Ｅ−Ｄにて漂白し、更にＰＦＩミルにて叩解し、
坪量６０ｇ／ｍ2の手すき紙を作成した。尚、Ｐの添加
率は１．０％、Ｅの添加率は０．５％で、反応温度は８
０℃、反応時間は２時間漂白した。Ｈの添加率は０．８
％、Ｅの添加率は０．２％で、反応温度は６５℃、反応
時間は２．５時間漂白した。Ｄの添加率は０．２５％
で、反応温度は７５℃、反応時間は３時間漂白した。実
施例１と同様のパルプ濃度で行った。(Example 5) The same pulp as in Example 1 was used.
20 U / g of SD enzyme as xylanase activity, 0.1% of Avos E-390 and 0.1% of NS206 (manufactured by Nissan Kagaku Co., Ltd., nonionic surfactant) as a surfactant were added and mixed at the same time to obtain a pulp concentration of 3. Adjusted to 5%, pH 6.5, 6
The reaction was performed at 0 ° C. for 1 hour. Then, wash and dehydrate, P / E
Bleached with -H / ED, beaten with PFI mill,
A handmade paper having a basis weight of 60 g / m 2 was prepared. The P addition rate was 1.0%, the E addition rate was 0.5%, and the reaction temperature was 8%.
Bleaching was carried out for 2 hours at 0 ° C. Addition rate of H is 0.8
%, E was 0.2%, the reaction temperature was 65 ° C., and the reaction time was 2.5 hours. Addition rate of D is 0.25%
The reaction temperature was 75 ° C., and the reaction time was bleaching for 3 hours. The same pulp concentration as in Example 1 was used.
【００３８】（実施例６）実施例１と同様のパルプに、
ＳＤ酵素をキシラナーゼ活性として２０Ｕ／ｇとアボス
Ｅ−３９０、プライマール８５０をともに０．１％同時
に添加混合し、パルプ濃度１２％に調製し、ｐＨ６．
５、６０℃で１時間反応させた。その後、洗浄脱水し、
Ｐ／Ｅ−Ｈ／Ｅ−Ｄにて漂白し、更にＰＦＩミルにて叩
解し、坪量６０ｇ／ｍ2の手すき紙を作成した。尚、Ｐ
の添加率は１．０％、Ｅの添加率は０．５％で、反応温
度は８０℃、反応時間は２時間漂白した。Ｈの添加率は
０．８％、Ｅの添加率は０．２％で、反応温度は６５
℃、反応時間は２．５時間漂白した。Ｄの添加率は０．
２５％で、反応温度は７５℃、反応時間は３時間漂白し
た。実施例１と同様のパルプ濃度で行った。Example 6 The same pulp as in Example 1 was used,
20 U / g of SD enzyme as xylanase activity, 0.1% of Avos E-390 and Primal 850 were added and mixed at the same time to prepare a pulp concentration of 12%, and a pH of 6.
The reaction was carried out at 5, 60 ° C. for 1 hour. After that, wash and dehydrate,
It was bleached with P / E-H / E-D and beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 . Note that P
The bleaching rate was 1.0%, the addition rate of E was 0.5%, the reaction temperature was 80 ° C., and the reaction time was 2 hours. The addition rate of H was 0.8%, the addition rate of E was 0.2%, and the reaction temperature was 65%.
Bleaching was carried out for 2.5 hours at ℃. The addition rate of D is 0.
At 25%, the reaction temperature was 75 ° C., and the reaction time was 3 hours. The same pulp concentration as in Example 1 was used.
【００３９】（実施例７）実施例１と同様のパルプに、
ＳＤ酵素をキシラナーゼ活性として８００Ｕ／ｇ、アボ
スＥ−３９０、プライマール８５０をともに１％同時に
添加混合し、パルプ濃度３．５％に調製し、ｐＨ８．
５、８０℃で１時間反応させた。その後、洗浄脱水し、
Ｐ／Ｅ−Ｈ／Ｅ−Ｄにて漂白し、更にＰＦＩミルにて叩
解し、坪量６０ｇ／ｍ2の手すき紙を作成した。尚、Ｐ
の添加率は１．０％、Ｅの添加率は０．５％で、反応温
度は８０℃、反応時間は２時間漂白した。Ｈの添加率は
０．８％、Ｅの添加率は０．２％で、反応温度は６５
℃、反応時間は２．５時間漂白した。Ｄの添加率は０．
２５％で、反応温度は７５℃、反応時間は３時間漂白し
た。実施例１と同様のパルプ濃度で行った。(Example 7) The same pulp as in Example 1 was used.
800 U / g of SD enzyme having xylanase activity, 1% of Avos E-390 and Primal 850 were simultaneously added and mixed to prepare a pulp concentration of 3.5%, and a pH of 8.
5, reacted at 80 ° C. for 1 hour. After that, wash and dehydrate,
It was bleached with P / E-H / E-D and beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 . Note that P
The bleaching rate was 1.0%, the addition rate of E was 0.5%, the reaction temperature was 80 ° C., and the reaction time was 2 hours. The addition rate of H was 0.8%, the addition rate of E was 0.2%, and the reaction temperature was 65%.
Bleaching was carried out for 2.5 hours at ℃. The addition rate of D is 0.
At 25%, the reaction temperature was 75 ° C., and the reaction time was 3 hours. The same pulp concentration as in Example 1 was used.
【００４０】（実施例８）実施例１と同様のパルプに、
ＳＤ酵素をキシラナーゼ活性として８００Ｕ／ｇ、アボ
スＥ−３９０、プライマール８５０をともに１％同時に
添加混合し、パルプ濃度３．５％に調製し、ｐＨ３．
５、３０℃で１時間反応させた。その後、洗浄脱水し、
Ｐ／Ｅ−Ｈ／Ｅ−Ｄにて漂白し、更にＰＦＩミルにて叩
解し、坪量６０ｇ／ｍ2の手すき紙を作成した。尚、Ｐ
の添加率は１．０％、Ｅの添加率は０．５％で、反応温
度は８０℃、反応時間は２時間漂白した。Ｈの添加率は
０．８％、Ｅの添加率は０．２％で、反応温度は６５
℃、反応時間は２．５時間漂白した。Ｄの添加率は０．
２５％で、反応温度は７５℃、反応時間は３時間漂白し
た。実施例１と同様のパルプ濃度で行った。(Example 8) The same pulp as in Example 1 was used.
800 U / g of SD enzyme as xylanase activity, 1% of Avos E-390, and Primal 850 were simultaneously added and mixed to prepare a pulp concentration of 3.5%, and a pH of 3.
Reaction was carried out at 5, 30 ° C. for 1 hour. After that, wash and dehydrate,
It was bleached with P / E-H / E-D and beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 . Note that P
The bleaching rate was 1.0%, the addition rate of E was 0.5%, the reaction temperature was 80 ° C., and the reaction time was 2 hours. The addition rate of H was 0.8%, the addition rate of E was 0.2%, and the reaction temperature was 65%.
Bleaching was carried out for 2.5 hours at ℃. The addition rate of D is 0.
At 25%, the reaction temperature was 75 ° C., and the reaction time was 3 hours. The same pulp concentration as in Example 1 was used.
【００４１】（実施例９）広葉樹（ユーカリ系約７０％
配合）の蒸解パルプ（カッパー価１７．１、粘度２８．
９ｃｐ、白色度２７．８％）に、酵素はＳＤ酵素をキシ
ラナーゼ活性として２０Ｕ／ｇとアボスＥ−３９０を
０．２％を同時に添加混合し、パルプ濃度３．５％に調
製し、ｐＨ６．５、６０℃で１時間反応させた。その
後、洗浄脱水し、ＯＢ（酸素漂白）−Ｐ／Ｅ−Ｈ／Ｅ−
Ｄにて漂白し、更にＰＦＩミルにて叩解し、坪量６０ｇ
／ｍ2の手すき紙を作成した。尚、Ｏ2の添加率は１．０
％、Ｅの添加率は０．５％で、反応温度は１１０℃、反
応時間は１時間漂白した。Ｐの添加率は１．０％、Ｅの
添加率は０．５％で、反応温度は８０℃、反応時間は２
時間漂白した。Ｈの添加率は０．８％、Ｅの添加率は
０．２％で、反応温度は６５℃、反応時間は２．５時間
漂白した。Ｄの添加率は０．２５％で、反応温度は７５
℃、反応時間は３時間漂白した。各漂白におけるパルプ
濃度は全て１２％にて行った。(Example 9) Broad-leaved tree (eucalyptus-based about 70%
Blended cooking pulp (kappa number 17.1, viscosity 28.
9 cp, whiteness 27.8%), 20 U / g of SD enzyme as a xylanase activity and 0.2% of Avos E-390 were simultaneously added and mixed to prepare a pulp concentration of 3.5%, and a pH of 6. The reaction was carried out at 5, 60 ° C. for 1 hour. After that, it is washed and dehydrated, and OB (oxygen bleaching) -P / E-H / E-
Bleached with D, beaten with a PFI mill, and weigh 60g.
/ M 2 handmade paper was made. The addition rate of O 2 is 1.0
%, E addition rate was 0.5%, the reaction temperature was 110 ° C., and the reaction time was bleaching for 1 hour. The P addition rate was 1.0%, the E addition rate was 0.5%, the reaction temperature was 80 ° C., and the reaction time was 2
Bleached for hours. The H content was 0.8%, the E content was 0.2%, the reaction temperature was 65 ° C., and the reaction time was 2.5 hours. The addition rate of D is 0.25% and the reaction temperature is 75.
Bleaching was carried out for 3 hours at ℃. The pulp concentration in each bleaching was all 12%.
【００４２】（実施例１０）実施例１の酵素処理時の洗
浄脱水した排水を酸素漂白の希釈水として使用し漂白し
たパルプ（カッパー価９．４、白色度４５．３％）を得
た。更に、実施例１と同じ条件で酵素処理し、その後洗
浄脱水しＰ／Ｅ−Ｈ／Ｅ−Ｄにて漂白し、ＰＦＩミルに
て叩解し、坪量６０ｇ／ｍ2の手すき紙を作成した。(Example 10) Pulp bleached (kappa number 9.4, whiteness 45.3%) was obtained by using the waste water that had been washed and dehydrated during the enzymatic treatment of Example 1 as dilution water for oxygen bleaching. Further, it was treated with an enzyme under the same conditions as in Example 1, then washed and dehydrated, bleached with P / E-H / ED, and beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 . .
【００４３】（実施例１１）実施例１と同様のパルプ
に、ＳＤ酵素をキシラナーゼ活性として２０Ｕ／ｇとア
ボスＥ−３９０を０．２％を同時に添加混合し、パルプ
濃度３．５％に調製し、ｐＨ５、５０℃で１時間反応さ
せた。その後、洗浄脱水し、Ｚ（オゾン）−Ｐ／Ｅにて
漂白し、更にＰＦＩミルにて叩解し、坪量６０ｇ／ｍ2
の手すき紙を作成した。尚、Ｚの添加率は０．５％で、
ｐＨ２、反応温度は２５℃、反応時間は０．５時間漂白
した。Ｐの添加率は０．３％、Ｅの添加率は０．１５％
で、反応温度は８０℃、反応時間は２時間漂白した。実
施例１と同様のパルプ濃度で行った。Example 11 To the same pulp as in Example 1, 20 U / g of SD enzyme having xylanase activity and 0.2% of Avos E-390 were simultaneously added and mixed to prepare a pulp concentration of 3.5%. Then, the mixture was reacted at pH 5 and 50 ° C. for 1 hour. Then, it was washed and dehydrated, bleached with Z (ozone) -P / E, and beaten with a PFI mill to obtain a basis weight of 60 g / m 2.
I made a handmade paper. The Z addition rate was 0.5%,
Bleaching was performed at pH 2, reaction temperature of 25 ° C., and reaction time of 0.5 hour. Addition rate of P is 0.3%, addition rate of E is 0.15%
The reaction temperature was 80 ° C. and the reaction time was bleaching for 2 hours. The same pulp concentration as in Example 1 was used.
【００４４】（実施例１２）実施例１と同様のパルプ
に、ＳＤ酵素をキシラナーゼ活性として２０Ｕ／ｇ、ア
ボスＥ−３９０、プライマール８５０をともに０．１％
同時に添加混合し、パルプ濃度３．５％に調製し、ｐＨ
５、５０℃で１時間反応させた。その後、洗浄脱水し、
Ｚ−Ｐ／Ｅにて漂白し、更にＰＦＩミルにて叩解し、坪
量６０ｇ／ｍ2の手すき紙を作成した。尚、Ｚの添加率
は０．５％で、反応温度は２５℃、反応時間は０．５時
間漂白した。Ｐの添加率は０．３％、Ｅの添加率は０．
１５％で、反応温度は８０℃、反応時間は２時間漂白し
た。実施例１と同様のパルプ濃度で行った。(Example 12) SD pulp having a xylanase activity of 20 U / g, Avos E-390 and Primal 850 were both added to a pulp similar to that of Example 1 in an amount of 0.1%.
Add and mix at the same time to adjust the pulp concentration to 3.5%, and adjust the pH.
The reaction was carried out at 5, 50 ° C. for 1 hour. After that, wash and dehydrate,
It was bleached with Z-P / E and further beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 . The Z addition rate was 0.5%, the reaction temperature was 25 ° C, and the reaction time was bleaching for 0.5 hours. The P addition rate was 0.3%, and the E addition rate was 0.
At 15%, the reaction temperature was 80 ° C., and the reaction time was 2 hours. The same pulp concentration as in Example 1 was used.
【００４５】（比較例１）実施例１と同様のパルプを、
酵素処理せずにＤ1（１回目の二酸化塩素処理）−Ｈ／
Ｅ−Ｄ2（２回目の二酸化塩素処理）にて漂白し、更に
ＰＦＩミルにて叩解し、坪量６０ｇ／ｍ2の手すき紙を
作成した。尚、Ｄ1の添加率は０．８％で、反応温度は
７５℃、反応時間は２時間漂白した。Ｈの添加率は０．
６％、Ｅの添加率は０．１％で、反応温度は６５℃、反
応時間は２．５時間漂白した。Ｄ2の添加率は０．３５
％で、反応温度は７５℃、反応時間は３時間漂白した。
実施例１と同様のパルプ濃度で行った。(Comparative Example 1) The same pulp as in Example 1 was used.
D1 (first chlorine dioxide treatment) without enzyme treatment-H /
Bleached by E-D2 (2 nd chlorine dioxide treatment), further beaten by PFI mill to prepare a handsheet having a basis weight of 60 g / m 2. The D1 addition rate was 0.8%, the reaction temperature was 75 ° C., and the reaction time was bleaching for 2 hours. The addition rate of H is 0.
The bleaching was performed at a reaction temperature of 65 ° C. for a reaction time of 2.5 hours. The addition rate of D2 is 0.35
%, The reaction temperature was 75 ° C., and the reaction time was bleaching for 3 hours.
The same pulp concentration as in Example 1 was used.
【００４６】（比較例２）実施例１と同様のパルプに、
ＳＤ酵素をキシラナーゼ活性として２０Ｕ／ｇ（対絶乾
パルプ）を加えて、パルプ濃度３．５％に調製し、ｐＨ
６．５、６０℃で１時間反応させた。その後、洗浄脱水
し、Ｄ1−Ｈ／Ｅ−Ｄ2にて漂白し、更にＰＦＩミルにて
叩解し、坪量６０ｇ／ｍ2の手すき紙を作成した。尚、
Ｄ1の添加率は０．８％で、反応温度は７５℃、反応時
間は２時間漂白した。Ｈの添加率は０．６％、Ｅの添加
率は０．１％で、反応温度は６５℃、反応時間は２．５
時間漂白した。Ｄ2の添加率は０．２％で、反応温度は
７５℃、反応時間は３時間漂白した。実施例１と同様の
パルプ濃度で行った。(Comparative Example 2) The same pulp as in Example 1 was used.
SD enzyme was added as xylanase activity to 20 U / g (versus dry pulp) to prepare a pulp concentration of 3.5%, and pH was adjusted.
The reaction was carried out at 6.5 and 60 ° C. for 1 hour. Thereafter, washing was dried, bleached with D1-H / E-D2, further beaten by PFI mill to prepare a handsheet having a basis weight of 60 g / m 2. still,
The addition rate of D1 was 0.8%, the reaction temperature was 75 ° C., and the reaction time was bleaching for 2 hours. The addition rate of H was 0.6%, the addition rate of E was 0.1%, the reaction temperature was 65 ° C, and the reaction time was 2.5.
Bleached for hours. The addition rate of D2 was 0.2%, the reaction temperature was 75 ° C., and the reaction time was bleaching for 3 hours. The same pulp concentration as in Example 1 was used.
【００４７】（比較例３）実施例１と同様のパルプに、
酵素はイルガザイム４０ｘ４（チバガイキー社製）をキ
シラナーゼ活性として２０Ｕ／ｇとアボスＥ−３９０を
０．２％同時に加えて、パルプ濃度３．５％に調製し、
ｐＨ６、６０℃で１時間反応させた。その後、洗浄脱水
し、Ｐ／Ｅ−Ｈ／Ｅ−Ｄにて漂白し、更にＰＦＩミルに
て叩解し、坪量６０ｇ／ｍ2の手すき紙を作成した。
尚、Ｐの添加率は１％で、Ｅの添加率は０．５％で反応
温度は７５℃、反応時間は２時間漂白した。Ｈの添加率
は０．８％、Ｅの添加率は０．２％で、反応温度は６５
℃、反応時間は２．５時間漂白した。Ｄの添加率は０．
３５％で、反応温度は７５℃、反応時間は３時間漂白し
た。実施例１と同様のパルプ濃度で行った。(Comparative Example 3) The same pulp as in Example 1 was used.
As an enzyme, Irugazyme 40x4 (manufactured by Ciba-Gaiki) was added as xylanase activity at 20 U / g and Avos E-390 at 0.2% at the same time to prepare a pulp concentration of 3.5%,
The reaction was carried out at pH 6 and 60 ° C. for 1 hour. Then, it was washed and dehydrated, bleached with P / E-H / E-D, and further beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 .
The P addition rate was 1%, the E addition rate was 0.5%, the reaction temperature was 75 ° C., and the reaction time was bleaching for 2 hours. The addition rate of H was 0.8%, the addition rate of E was 0.2%, and the reaction temperature was 65%.
Bleaching was carried out for 2.5 hours at ℃. The addition rate of D is 0.
At 35%, the reaction temperature was 75 ° C. and the reaction time was bleaching for 3 hours. The same pulp concentration as in Example 1 was used.
【００４８】（比較例４）実施例１と同様のパルプに、
酵素はベッセレックス（合同酒精社製）をキシラナーゼ
活性として２０Ｕ／ｇとアボスＥ−３９０を０．２％同
時に加えて、パルプ濃度３．５％に調製し、ｐＨ５、５
５℃で１時間反応させた。その後、洗浄脱水し、Ｐ／Ｅ
−Ｈ／Ｅ−Ｄにて漂白し、更にＰＦＩミルにて叩解し、
坪量６０ｇ／ｍ2の手すき紙を作成した。尚、Ｐの添加
率は１％で、Ｅの添加率は０．５％で反応温度は７５
℃、反応時間は２時間漂白した。Ｈの添加率は０．８
％、Ｅの添加率は０．２％で、反応温度は６５℃、反応
時間は２．５時間漂白した。Ｄの添加率は０．３５％
で、反応温度は７５℃、反応時間は３時間漂白した。実
施例１と同様のパルプ濃度で行った。(Comparative Example 4) The same pulp as in Example 1 was used.
As the enzyme, Vesselex (manufactured by Godo Shusei Co., Ltd.) was added as xylanase activity at 20 U / g and Avos E-390 at 0.2% at the same time to prepare a pulp concentration of 3.5%, and the pH was adjusted to 5, 5
The reaction was carried out at 5 ° C for 1 hour. Then, wash and dehydrate, P / E
Bleached with -H / ED, beaten with PFI mill,
A handmade paper having a basis weight of 60 g / m 2 was prepared. The P addition rate was 1%, the E addition rate was 0.5%, and the reaction temperature was 75%.
Bleaching was carried out for 2 hours at 0 ° C. Addition rate of H is 0.8
%, E was 0.2%, the reaction temperature was 65 ° C., and the reaction time was 2.5 hours. Addition rate of D is 0.35%
The reaction temperature was 75 ° C., and the reaction time was bleaching for 3 hours. The same pulp concentration as in Example 1 was used.
【００４９】（比較例５）実施例１と同様のパルプに、
酵素はパルプザイムＨＡ（ＮＯＶＯ社製）をキシラナー
ゼ活性として２０Ｕ／ｇとアボスＥ−３９０を０．２％
同時に加えて、パルプ濃度３．５％に調製し、ｐＨ５．
５、５５℃で１時間反応させた。その後、洗浄脱水し、
Ｐ／Ｅ−Ｈ／Ｅ−Ｄにて漂白し、更にＰＦＩミルにて叩
解し、坪量６０ｇ／ｍ2の手すき紙を作成した。尚、Ｐ
の添加率は１％で、Ｅの添加率は０．５％で反応温度は
７５℃、反応時間は２時間漂白した。Ｈの添加率は０．
８％、Ｅの添加率は０．２％で、反応温度は６５℃、反
応時間は２．５時間漂白した。Ｄの添加率は０．３５％
で、反応温度は７５℃、反応時間は３時間漂白した。実
施例１と同様のパルプ濃度で行った。(Comparative Example 5) A pulp similar to that of Example 1 was prepared.
The enzyme was pulpzyme HA (manufactured by NOVO) as xylanase activity of 20 U / g and Avos E-390 of 0.2%.
At the same time, the pulp concentration was adjusted to 3.5% and the pH was adjusted to 5.
The reaction was carried out at 5, 55 ° C for 1 hour. After that, wash and dehydrate,
It was bleached with P / E-H / E-D and beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 . Note that P
The bleaching rate was 1%, the addition rate of E was 0.5%, the reaction temperature was 75 ° C., and the reaction time was 2 hours. The addition rate of H is 0.
The bleaching rate was 8%, the addition rate of E was 0.2%, the reaction temperature was 65 ° C., and the reaction time was 2.5 hours. Addition rate of D is 0.35%
The reaction temperature was 75 ° C., and the reaction time was bleaching for 3 hours. The same pulp concentration as in Example 1 was used.
【００５０】（比較例６）実施例１と同様のパルプに、
イルガザイム４０ｘ４をキシラナーゼ活性２０Ｕ／ｇと
アボスＥー３９０を０．２％同時に加えて、パルプ濃度
３．５％に調製し、ｐＨ６、６０℃で１時間反応させ
た。その後、洗浄脱水し、Ｚ−Ｐ／Ｅにて漂白し、更に
ＰＦＩミルにて叩解し、坪量６０ｇ／ｍ2の手すき紙を
作成した。尚、Ｚの添加率は０．５％で、反応温度は２
５℃、反応時間は０．５時間漂白した。Ｐの添加率は
０．４％、Ｅの添加率は０．２％で、反応温度は８０
℃、反応時間は２時間漂白した。実施例１と同様のパル
プ濃度で行った。(Comparative Example 6) A pulp similar to that of Example 1 was prepared.
Irugazyme 40x4 was added to 20 U / g of xylanase activity and 0.2% of Avos E-390 at the same time to prepare a pulp concentration of 3.5%, and reacted at pH 6 and 60 ° C for 1 hour. Then, it was washed and dehydrated, bleached with Z-P / E, and beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 . The addition rate of Z was 0.5% and the reaction temperature was 2%.
Bleaching was carried out at 5 ° C for a reaction time of 0.5 hours. The P addition rate is 0.4%, the E addition rate is 0.2%, and the reaction temperature is 80%.
Bleaching was carried out for 2 hours at 0 ° C. The same pulp concentration as in Example 1 was used.
【００５１】（比較例７）実施例１と同様のパルプに、
ベッセレックスをキシラナーゼ活性として２０Ｕ／ｇと
アボスＥ−３９０を０．２％同時に加えて、パルプ濃度
３．５％に調製し、ｐＨ５、５５℃で１時間反応させ
た。その後、洗浄脱水し、Ｚ−Ｐ／Ｅにて漂白し、更に
ＰＦＩミルにて叩解（３０００ｒｐｍ）し、坪量６０ｇ
／ｍ2の手すき紙を作成した。尚、Ｚの添加率は０．５
％で、反応温度は２５℃、反応時間は０．５時間漂白し
た。Ｐの添加率は０．５％、Ｅの添加率は０．２％で、
反応温度は８０℃、反応時間は２時間漂白した。実施例
１と同様のパルプ濃度で行った。(Comparative Example 7) A pulp similar to that of Example 1 was prepared.
20 U / g of Vesselex as xylanase activity and 0.2% of Avos E-390 were simultaneously added to prepare a pulp concentration of 3.5%, and the mixture was reacted at pH 5 and 55 ° C. for 1 hour. Then, it was washed and dehydrated, bleached with Z-P / E, beaten with a PFI mill (3000 rpm), and weighed 60 g.
/ M 2 handmade paper was made. The Z addition rate is 0.5
%, The reaction temperature was 25 ° C., and the reaction time was 0.5 hour. Addition rate of P is 0.5%, addition rate of E is 0.2%,
The reaction temperature was 80 ° C., and the reaction time was bleaching for 2 hours. The same pulp concentration as in Example 1 was used.
【００５２】（比較例８）実施例１と同様のパルプに、
パルプザイムＨＡをキシラナーゼ活性として２０Ｕ／ｇ
とアボスＥ−３９０を０．２％同時に加えて、パルプ濃
度３．５％に調製し、ｐＨ５、５５℃で１時間反応させ
た。その後、洗浄脱水し、Ｚ−Ｐ／Ｅにて漂白し、更に
ＰＦＩミルにて叩解し、坪量６０ｇ／ｍ2の手すき紙を
作成した。尚、Ｚの添加率は０．５％で、反応温度は２
５℃、反応時間は０．５時間漂白した。Ｐの添加率は
０．５％、Ｅの添加率は０．２％で、反応温度は８０
℃、反応時間は２時間漂白した。実施例１と同様のパル
プ濃度で行った。(Comparative Example 8) A pulp similar to that of Example 1 was prepared.
Pulpzyme HA with xylanase activity of 20 U / g
0.2% of Avos E-390 was added at the same time to adjust the pulp concentration to 3.5%, and the mixture was reacted at pH 5 and 55 ° C. for 1 hour. Then, it was washed and dehydrated, bleached with Z-P / E, and beaten with a PFI mill to prepare a handmade paper having a basis weight of 60 g / m 2 . The addition rate of Z was 0.5% and the reaction temperature was 2%.
Bleaching was carried out at 5 ° C for a reaction time of 0.5 hours. The P addition rate is 0.5%, the E addition rate is 0.2%, and the reaction temperature is 80%.
Bleaching was carried out for 2 hours at 0 ° C. The same pulp concentration as in Example 1 was used.
【００５３】[0053]
【表１】 [Table 1]
【００５４】[0054]
【表２】 [Table 2]
【００５５】尚、カッパー価は酸素漂白→酵素処理後、
又は酵素処理→酸素漂白後の値である。更に、酵素、過
酸化水素、オゾン段の排水は系内に回収するため、ＡＯ
Ｘ、ＣＯＤ、色度の値は除いたものである。The kappa number is oxygen bleaching → after enzyme treatment,
Or the value after enzyme treatment → oxygen bleaching. Furthermore, since the enzyme, hydrogen peroxide, and ozone stage wastewater are collected in the system, AO
The values of X, COD, and chromaticity are excluded.
【００５６】表１、２の実施例１〜１１と比較例１〜８
から、本発明は、従来の酵素（イルガザイム、ベッセレ
ックス、パルプザイム）を使用した場合や無添加の場合
に比べて、易叩解、高白色度、高粘度の非塩素漂白パル
プが得られることが判る。又、キレート剤や界面活性剤
を添加することによってより改善されていることが判
る。更に、ＡＯＸ、ＣＯＤ、色度が酵素無添加に比べて
かなり低減されていることが判る。又、紙の物性におい
ても高平滑、高強度であり、且つ叩解による繊維のフィ
ブリル化が促進されベッセルピックが大幅に減少するこ
とが判る。Examples 1 to 11 and Comparative Examples 1 to 8 in Tables 1 and 2
From the results, it can be seen that the present invention provides a non-chlorine bleached pulp with easy beating, high whiteness and high viscosity, as compared with the case of using the conventional enzyme (Irgazyme, Vesselex, pulpzyme) and the case of no addition. . Further, it can be seen that the addition is improved by adding a chelating agent or a surfactant. Further, it can be seen that AOX, COD and chromaticity are considerably reduced as compared with the case where no enzyme is added. Further, it can be seen that the physical properties of paper are also high smoothness and high strength, and the fibrillation of fibers by beating is promoted, and the vessel picking is greatly reduced.
【００５７】[0057]
【発明の効果】本発明の化学パルプの漂白法及び改質法
において、蒸解あるいは酸素漂白後の化学パルプにＳＤ
酵素とキレート剤による同時処理、又は界面活性剤とキ
レート剤と酵素の同時処理の後漂白し、叩解することに
よって脱リグニンの効果を進めるだけでなく、叩解性が
促進しベッセルピックも改善される。更に収率の低下及
び粘度の低下、引裂強度の低下を防止するだけでなく、
平滑性、裂断長、内部結合が向上する傾向にある。尚、
この方法により漂白薬品の添加量が少なく済むだけでな
く、ＡＯＸ、ＣＯＤ、色度の低減効果が見られる。INDUSTRIAL APPLICABILITY In the bleaching method and reforming method of the chemical pulp of the present invention, SD is added to the chemical pulp after cooking or oxygen bleaching.
Simultaneous treatment with enzyme and chelating agent, or simultaneous treatment with surfactant, chelating agent and enzyme, not only promotes delignification effect by bleaching and beating, but also enhances beating property and improves vessel picking. . Furthermore, it not only prevents lowering of yield and viscosity and lowering of tear strength, but also
Smoothness, breaking length, and internal bonding tend to improve. still,
This method not only reduces the amount of bleaching chemicals to be added, but also has the effect of reducing AOX, COD, and chromaticity.
フロントページの続き (72)発明者 原 普一 東京都千代田区丸の内３丁目４番２号 三 菱製紙株式会社内 (72)発明者 埜口 能孝 千葉県千葉市緑区大野台１丁目１番１号 昭和電工株式会社総合研究所内Front Page Continuation (72) Inventor Fuichi Hara, 3-4-2 Marunouchi, Chiyoda-ku, Tokyo Sanryo Paper Co., Ltd. (72) 1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture Showa Denko Co., Ltd.
Claims (5)
バチルスｓｐ．ＳＤ９０２株由来の酵素とキレート剤の
同時処理、又は界面活性剤とキレート剤と該酵素による
同時処理の後に漂白し叩解することを特徴とする化学パ
ルプの漂白法及び改質法。1. A chemical pulp after digestion or oxygen bleaching has Bacillus sp. A method for bleaching and modifying a chemical pulp, which comprises bleaching and beating after simultaneous treatment of an SD902 strain-derived enzyme and a chelating agent, or simultaneous treatment with a surfactant, a chelating agent and the enzyme.
３〜９、処理温度は２０〜９０℃、処理時間は１５〜１
８０分、パルプ濃度は２〜１５重量％で、酵素の添加量
はキシラナーゼ活性として０．１〜１０００Ｕ／ｇ（対
絶乾パルプ）で、キレート剤又はキレート剤と界面活性
剤を添加する場合は添加量がともに０．０１〜５重量％
（対絶乾パルプ）であることを特徴とする請求項１記載
の化学パルプの漂白法及び改質法。2. The processing conditions according to claim 1, wherein the processing pH is 3 to 9, the processing temperature is 20 to 90 ° C., and the processing time is 15 to 1.
80 minutes, pulp concentration is 2 to 15% by weight, the amount of enzyme added is 0.1 to 1000 U / g (vs. dry pulp) as xylanase activity, and when a chelating agent or a chelating agent and a surfactant are added, Addition amount is 0.01 to 5% by weight
The method for bleaching and reforming chemical pulp according to claim 1, wherein the method is a dry pulp.
らなるキレート剤、および高分子の塩からなるキレート
剤よりなる群より選んだ少なくとも一種、該界面活性剤
が、ノニオン性、カチオン性、アニオン性、両性の有機
又は高分子の界面活性剤よりなる群より選んだ少なくと
も一種であることを特徴とする請求項１記載の化学パル
プの漂白法及び改質法。3. The chelating agent is at least one selected from the group consisting of a chelating agent composed of an organic salt containing nitrogen and a chelating agent composed of a polymeric salt, and the surfactant is a nonionic or cationic one. The method for bleaching and modifying a chemical pulp according to claim 1, which is at least one selected from the group consisting of anionic or amphoteric organic or polymeric surfactants.
時処理、又は該界面活性剤と該キレート剤と該酵素同時
処理の白水を向流的に前の処理段に戻し、最終的に黒液
回収工程に送ることを特徴とする請求項１、２、又は３
記載の化学パルプの漂白法及び改質法。4. The white water of the chelating agent and the enzyme simultaneous treatment according to claim 1, or the surfactant, the chelating agent and the enzyme simultaneous treatment of the surfactant, is countercurrently returned to a preceding treatment stage, and finally. It sends to a black liquor collection process, It is characterized by the above-mentioned.
A method for bleaching and modifying a chemical pulp as described.
塩素、次亜塩素酸塩、オゾン、過酸化物、過酸化物と酸
素、及び二酸化チオ尿素よりなる群より選んだ少なくと
も一種にて漂白することを特徴とする請求項１、２、３
又は４記載の化学パルプの漂白法及び改質法。5. The bleaching method according to claim 1, wherein at least one selected from the group consisting of chlorine dioxide, hypochlorite, ozone, peroxide, peroxide and oxygen, and thiourea dioxide is bleached. It is characterized by the above-mentioned.
Or a method for bleaching and modifying a chemical pulp according to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18014395A JPH0931880A (en) | 1995-07-17 | 1995-07-17 | Bleaching and modification of chemical pulp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18014395A JPH0931880A (en) | 1995-07-17 | 1995-07-17 | Bleaching and modification of chemical pulp |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0931880A true JPH0931880A (en) | 1997-02-04 |
Family
ID=16078163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18014395A Pending JPH0931880A (en) | 1995-07-17 | 1995-07-17 | Bleaching and modification of chemical pulp |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0931880A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1053997A (en) * | 1996-07-31 | 1998-02-24 | Oji Paper Co Ltd | Production of coated paper for printing |
| US6341836B1 (en) | 1999-03-17 | 2002-01-29 | Fujitsu Limited | Water-repellent coating and method for forming same on the surface of liquid jet |
| WO2007140838A2 (en) * | 2006-06-08 | 2007-12-13 | Voith Patent Gmbh | Lignocellulosic fibrous material made of wood |
| WO2007140839A3 (en) * | 2006-06-08 | 2008-03-27 | Voith Patent Gmbh | Method for producing fibrous material made of wood |
| WO2007140837A3 (en) * | 2006-06-08 | 2008-04-03 | Voith Patent Gmbh | Method for producing fibrous material |
| WO2008077450A1 (en) * | 2006-12-23 | 2008-07-03 | Voith Patent Gmbh | Method for the production of tissue paper |
| WO2008138429A1 (en) * | 2007-05-11 | 2008-11-20 | Voith Patent Gmbh | Lignocellulose fibre consisting of wood |
| JP2021518492A (en) * | 2018-03-15 | 2021-08-02 | バックマン ラボラトリーズ インターナショナル，インコーポレイティド | Methods and systems for producing market pulp and their products |
-
1995
- 1995-07-17 JP JP18014395A patent/JPH0931880A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1053997A (en) * | 1996-07-31 | 1998-02-24 | Oji Paper Co Ltd | Production of coated paper for printing |
| US6341836B1 (en) | 1999-03-17 | 2002-01-29 | Fujitsu Limited | Water-repellent coating and method for forming same on the surface of liquid jet |
| WO2007140838A2 (en) * | 2006-06-08 | 2007-12-13 | Voith Patent Gmbh | Lignocellulosic fibrous material made of wood |
| WO2007140839A3 (en) * | 2006-06-08 | 2008-03-27 | Voith Patent Gmbh | Method for producing fibrous material made of wood |
| WO2007140838A3 (en) * | 2006-06-08 | 2008-03-27 | Voith Patent Gmbh | Lignocellulosic fibrous material made of wood |
| WO2007140837A3 (en) * | 2006-06-08 | 2008-04-03 | Voith Patent Gmbh | Method for producing fibrous material |
| US8152960B2 (en) | 2006-06-08 | 2012-04-10 | Voith Patent Gmbh | Lignocellulosic fibrous material made of wood |
| US8758557B2 (en) | 2006-06-08 | 2014-06-24 | Voith Patent Gmbh | Process for producing fibrous material from wood |
| WO2008077450A1 (en) * | 2006-12-23 | 2008-07-03 | Voith Patent Gmbh | Method for the production of tissue paper |
| WO2008138429A1 (en) * | 2007-05-11 | 2008-11-20 | Voith Patent Gmbh | Lignocellulose fibre consisting of wood |
| JP2021518492A (en) * | 2018-03-15 | 2021-08-02 | バックマン ラボラトリーズ インターナショナル，インコーポレイティド | Methods and systems for producing market pulp and their products |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4568420A (en) | Multi-stage bleaching process including an enhanced oxidative extraction stage | |
| RU2126862C1 (en) | Method of removing groups of hexenuronic acids from cellulose by heat treatment | |
| CA2067295C (en) | Process for bleaching of lignocellulose-containing material | |
| CA2115881C (en) | Non-chlorine bleaching of kraft pulp | |
| EP1095184A1 (en) | Method of producing lignocellulosic pulp from non-woody species | |
| NZ242465A (en) | Delignification and bleaching of chemical pulp with acid and a magnesium | |
| JP2007530818A (en) | Methods for optimizing pulp whiteness enhancement and use of bleaching chemicals | |
| CA2121387C (en) | Method for bleaching lignocellulose-containing pulp | |
| US5639348A (en) | Bleaching compositions comprising sulfamates and borates or gluconates and processes | |
| JPH0931880A (en) | Bleaching and modification of chemical pulp | |
| CA2079000C (en) | Method for the use of enzymes in processing and bleaching of paper pulp, and apparatus for use thereof | |
| CA2432788C (en) | Alkaline extraction stages comprising xylanase | |
| RU2439232C2 (en) | Method of bleaching paper pulp by final ozone treatment at high temperature | |
| AU653467B2 (en) | Bleaching of sulphate pulp | |
| JPH08246368A (en) | Enzymatic treatment of chemical pulp | |
| AU671337B2 (en) | Process for bleaching of lignocellulose-containing pulp | |
| JP3697335B2 (en) | Treatment of chemical pulp with acidic bleached white water | |
| WO1992007998A1 (en) | Method for bleaching pulp | |
| JPH08337989A (en) | Production of non-chlorine-bleached pulp and treatment of bleached waste water | |
| JP2001192991A (en) | Method of bleaching alkali pulp | |
| JPH11279968A (en) | Bleaching pretreatment of hardwood chemical pulp | |
| NZ250050A (en) | Bleaching pulp; magnesium compound pretreatment in acid conditions | |
| JPH07173785A (en) | Method for bleaching chemical pulp with peroxide or ozone | |
| WO1993007332A1 (en) | Method for enzymatic treatment of lignocellulosic materials, in particular cellulose pulps | |
| JPH06166978A (en) | Production of bleached hemp pulp |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Effective date: 20040330 Free format text: JAPANESE INTERMEDIATE CODE: A02 |