JP2014034753A - Papermaking additive and method of producing the same - Google Patents
Papermaking additive and method of producing the same Download PDFInfo
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この発明は、セルロースを分解したセルロース解重合物からなる製紙用添加剤に関する。 The present invention relates to a paper additive comprising a cellulose depolymerized product obtained by decomposing cellulose.
従来から、紙の強度を高める目的で製紙用添加剤が抄紙工程にてパルプスラリーに添加され、用いられている。この製紙用添加剤としては、変性デンプン、ポリアクリルアミド、ポリアミド、ポリアミド−エピクロルヒドリン樹脂、メラミン−ホルムアルデヒド樹脂、尿素−ホルムアルデヒド樹脂等が挙げられる。 Conventionally, for the purpose of increasing the strength of paper, a papermaking additive is added to a pulp slurry in a papermaking process and used. Examples of the paper additive include modified starch, polyacrylamide, polyamide, polyamide-epichlorohydrin resin, melamine-formaldehyde resin, urea-formaldehyde resin, and the like.
ところで、これらの製紙用添加剤は、紙力増強効果が低かったり、高価であったり、あるいは抄造条件によっては歩留りが悪く添加量に見合う十分な紙力増強効果が得られない等、種々の問題点を有しており、十分に満足し得るものではない。 By the way, these papermaking additives have various problems such as low paper strength enhancement effect, high cost, or poor yield due to papermaking conditions, and insufficient paper strength enhancement effect corresponding to the amount added. It has a point and is not fully satisfactory.
これに対し、カルボキシメチルセルロース（以下、「ＣＭＣ」という。）やカルボキシエチルセルロース（以下、「ＣＥＣ」という。）を添加した後、鉱酸を添加してＣＭＣやＣＥＣを酸型へ変換することによって溶解性を落とし、パルプに定着させる方法が検討されている（特許文献１）。 On the other hand, after adding carboxymethyl cellulose (hereinafter referred to as “CMC”) or carboxyethyl cellulose (hereinafter referred to as “CEC”), it is dissolved by adding mineral acid to convert CMC or CEC into an acid form. A method of reducing the property and fixing to pulp has been studied (Patent Document 1).
また、アミノ基含有アルキルクロライド及びクロロ硫酸等を用いて、セルロースにアミノ基及びスルホン酸基を導入した紙力増強剤が検討されている（引用文献２）。 Further, a paper strength enhancer in which an amino group and a sulfonic acid group are introduced into cellulose using an amino group-containing alkyl chloride, chlorosulfuric acid, or the like has been studied (Cited document 2).
しかしながら、前者においては、ＣＭＣやＣＥＣを製紙用添加剤として用いたとしても、得られる紙力増強効果が小さく、又硫酸バンドを添加併用しなければ紙に歩留らないため、効果を発現しない等の問題点を有する。 However, in the former, even if CMC or CEC is used as an additive for papermaking, the effect of enhancing the paper strength obtained is small, and it does not yield on paper unless a sulfuric acid band is added in combination, so that the effect is not manifested. And so on.
また、後者においては、複数種の塩素化合物を使用する必要があり、製造工程が複雑になると共に、塩化物の排出物の処理が必要となる。また、アミノ基及びスルホン酸基の置換度があまり上がらないため、紙力増強効果が十分に得られないおそれがある。 In the latter case, it is necessary to use a plurality of types of chlorine compounds, which complicates the manufacturing process and requires treatment of chloride emissions. Moreover, since the substitution degree of an amino group and a sulfonic acid group does not increase so much, there is a possibility that the paper strength enhancing effect cannot be obtained sufficiently.
そこでこの発明は、十分な紙力増強効果を有し、かつ、簡便に製紙用添加剤を得ることを目的とする。 Therefore, an object of the present invention is to obtain a papermaking additive simply and having a sufficient paper strength enhancing effect.
この発明は、負電荷が−２〜−０．３ｍｅｑ／ｇ・ｓｏｌｉｄ、重量平均分子量が２０００〜３００００のセルロース解重合物からなる製紙用添加剤を用いることにより、上記の課題を解決したのである。 This invention has solved the above problems by using a paper additive made of a cellulose depolymerized product having a negative charge of −2 to −0.3 meq / g · solid and a weight average molecular weight of 2000 to 30000. .
この製紙用添加剤は、セルロースを主成分とするバイオマス原料を０〜２０℃で０．５〜２時間、７２〜８５重量％の硫酸水溶液中で処理することにより製造することができる。 This papermaking additive can be produced by treating a biomass raw material mainly composed of cellulose at 0 to 20 ° C. for 0.5 to 2 hours in a 72 to 85% by weight sulfuric acid aqueous solution.
この発明により、負電荷の大きい製紙用添加剤を簡便に得ることができ、カチオン性製紙用添加剤を併用することにより、十分な紙力増強効果を発揮することができる。 According to the present invention, a papermaking additive having a large negative charge can be easily obtained, and a sufficient paper strength enhancing effect can be exhibited by using the cationic papermaking additive in combination.
以下、この発明について詳細に説明する。
この発明は、セルロース解重合物からなる製紙用添加剤に関する。
The present invention will be described in detail below.
The present invention relates to a papermaking additive comprising a cellulose depolymerized product.
上記セルロース解重合物は、セルロースを主成分とするバイオマス原料を解重合することにより得られ、元のセルロースより重合度が低下したものである。なお、「セルロースを主成分とするバイオマス原料」とは、バイオマス原料中において、含有する水を除いた場合にセルロースの含有割合が最大であることを意味する。このセルロースを主成分とするバイオマス原料としては、セルロース、古紙等の紙類、パルプ、稲わら、バガス等のセルロース含有のバイオマスや、製紙スラッジ等のセルロース系廃棄物等を例として挙げることができる。セルロース解重合物はα−グリコシド結合でなく、β−グリコシド結合を有し、パルプと同様の構造をもつため歩留りが向上し、剛直性を有するため、紙力増強効果の向上に寄与することができる。 The said cellulose depolymerization thing is obtained by depolymerizing the biomass raw material which has a cellulose as a main component, and a polymerization degree falls from the original cellulose. In addition, "the biomass raw material which has a cellulose as a main component" means that the content rate of a cellulose is the largest in the biomass raw material, when the water to contain is remove | excluded. Examples of biomass raw materials mainly composed of cellulose include cellulose, paper such as used paper, cellulose-containing biomass such as pulp, rice straw, and bagasse, and cellulosic waste such as papermaking sludge. . Cellulose depolymerized products have β-glycoside bonds, not α-glycosidic bonds, and have the same structure as pulp, so that the yield is improved and they have rigidity, which can contribute to the improvement of paper strength enhancing effect. it can.
上記のセルロースを主成分とするバイオマス原料の解重合は、所定の硫酸水溶液中で、所定温度、所定時間の条件下で反応させることにより行うことができる。所定の条件下において所定の硫酸水溶液中で解重合を行うので、得られる解重合物に、スルホン酸基が導入され、負電荷が付与される。 Depolymerization of the biomass raw material mainly composed of cellulose can be performed by reacting in a predetermined sulfuric acid aqueous solution under conditions of a predetermined temperature and a predetermined time. Since depolymerization is performed in a predetermined aqueous sulfuric acid solution under predetermined conditions, a sulfonic acid group is introduced into the resulting depolymerized product and a negative charge is imparted.
上記の硫酸水溶液の硫酸濃度は、７２重量％以上がよく、７５重量％以上が好ましい。７２重量％より低いと、十分な量のスルホン酸基を導入することができず、得られる負電荷を所定以上とすることができないため、カチオン性製紙用添加剤と併用した場合でもパルプへの定着が悪くなり、十分な紙力増強効果を得られなくなるおそれがある。一方、硫酸濃度の上限は、８５重量％がよく、８０重量％が好ましい。８５重量％より高いと、上記セルロースを主成分とするバイオマス原料の炭化、もしくは解重合物の過分解が生じてしまい、解重合物が得られなくなるおそれがある。 The sulfuric acid concentration in the aqueous sulfuric acid solution is preferably 72% by weight or more, and preferably 75% by weight or more. If it is lower than 72% by weight, a sufficient amount of the sulfonic acid group cannot be introduced, and the resulting negative charge cannot be increased to a predetermined value or more. Therefore, even when used in combination with a cationic papermaking additive, Fixing may be worsened and a sufficient paper strength enhancing effect may not be obtained. On the other hand, the upper limit of the sulfuric acid concentration is preferably 85% by weight, and preferably 80% by weight. If it is higher than 85% by weight, carbonization of the biomass raw material containing cellulose as a main component or excessive decomposition of the depolymerized product may occur, and the depolymerized product may not be obtained.
上記の反応温度は、２０℃以下がよく、１０℃以下が好ましい。２０℃より高いと、スルホン酸基が導入される前に、セルロースの解重合反応が優先的に進行し、得られるセルロース解重合物中のスルホン酸基量が少なくなってしまい、得られる負電荷を所定以上とすることができないため、カチオン性製紙用添加剤と併用した場合でもパルプへの定着が悪くなり、十分な紙力増強効果を得られなくなるおそれがある。一方、反応温度の下限は、特に限定されないが、解重合反応の進行の程度から、０℃以上である方が好ましい。 The reaction temperature is preferably 20 ° C. or less, and preferably 10 ° C. or less. When the temperature is higher than 20 ° C., the depolymerization reaction of cellulose proceeds preferentially before the sulfonic acid groups are introduced, and the amount of sulfonic acid groups in the resulting cellulose depolymerized product decreases, resulting in a negative charge. Therefore, even when it is used in combination with a cationic papermaking additive, the fixing to the pulp is worsened, and there is a possibility that a sufficient paper strength enhancing effect cannot be obtained. On the other hand, the lower limit of the reaction temperature is not particularly limited, but is preferably 0 ° C. or higher from the degree of progress of the depolymerization reaction.
上記の反応時間は、上記の反応温度により選択されるが、０．５時間以上がよく、１時間以上が好ましい。０．５時間より短いと、解重合反応が十分に進行しなくなるおそれがある。一方、反応時間の上限は、特に限定されないが、解重合物がさらに過分解するおそれがあるため、２時間以下が好ましい。 The above reaction time is selected depending on the above reaction temperature, but it is preferably 0.5 hour or longer, and preferably 1 hour or longer. If it is shorter than 0.5 hour, the depolymerization reaction may not proceed sufficiently. On the other hand, the upper limit of the reaction time is not particularly limited, but is preferably 2 hours or less because the depolymerized product may be further excessively decomposed.
上記解重合で得られるセルロース解重合物の重量平均分子量は、２０００以上がよく、５０００以上が好ましい。２０００より小さいと、十分な紙力増強効果を得られなくなるおそれがある。一方、重量平均分子量の上限は、３００００がよく、２５０００が好ましい。３００００より大きいと、解重合物の水溶性が低くなり、解重合反応時に十分な量の解重合物が得られないという問題点を生じる場合がある。 The weight average molecular weight of the cellulose depolymerized product obtained by the above depolymerization is preferably 2000 or more, and preferably 5000 or more. If it is less than 2000, there is a possibility that a sufficient paper strength enhancing effect cannot be obtained. On the other hand, the upper limit of the weight average molecular weight is preferably 30000 and preferably 25000. If it is greater than 30000, the water solubility of the depolymerized product will be low, and there may be a problem that a sufficient amount of depolymerized product cannot be obtained during the depolymerization reaction.
上記解重合で得られるセルロース解重合物の負電荷の量は、−０．３ｍｅｑ／ｇ・ｓｏｌｉｄ以下（電荷の絶対値で、０．３ｍｅｑ／ｇ・ｓｏｌｉｄ以上）がよく、−０．５ｍｅｑ／ｇ・ｓｏｌｉｄ以下（電荷の絶対値で、０．５ｍｅｑ／ｇ・ｓｏｌｉｄ以上）が好ましい。負電荷の量が、−０．３ｍｅｑ／ｇ・ｓｏｌｉｄより大きい（電荷の絶対値で、０．３ｍｅｑ／ｇ・ｓｏｌｉｄより小さい）と、カチオン性製紙用添加剤と併用した場合でもパルプへの定着が悪くなり、十分な紙力増強効果を得られなくなるおそれがある。一方、負電荷の量の下限（電荷の絶対値の上限）は、−２ｍｅｑ／ｇ・ｓｏｌｉｄ（電荷の絶対値で、２ｍｅｑ／ｇ・ｓｏｌｉｄ）がよく、−１．５ｍｅｑ／ｇ・ｓｏｌｉｄ（電荷の絶対値で、１．５ｍｅｑ／ｇ・ｓｏｌｉｄ）が好ましい。負電荷の量が、−２ｍｅｑ／ｇ・ｓｏｌｉｄより小さい（電荷の絶対値で、２ｍｅｑ／ｇ・ｓｏｌｉｄより大きい）と、使用するカチオン性製紙用添加剤の種類によっては、カチオン基がすべて電気的に中性となりパルプへの定着が起こらず、紙力増強効果が得られないという問題点を生じる場合がある。 The amount of negative charge of the cellulose depolymerized product obtained by the above depolymerization is preferably −0.3 meq / g · solid or less (the absolute value of the charge is 0.3 meq / g · solid or more), and −0.5 meq / g · solid or less (absolute value of charge, 0.5 meq / g · solid or more) is preferable. When the amount of negative charge is larger than −0.3 meq / g · solid (the absolute value of charge is smaller than 0.3 meq / g · solid), it is fixed to pulp even when used in combination with a cationic papermaking additive. May deteriorate, and a sufficient paper strength enhancing effect may not be obtained. On the other hand, the lower limit of the negative charge amount (upper limit of the absolute value of the charge) is preferably −2 meq / g · solid (the absolute value of the charge is 2 meq / g · solid), and −1.5 meq / g · solid (charge) Of 1.5 meq / g · solid). If the amount of negative charge is less than −2 meq / g · solid (the absolute value of charge is greater than 2 meq / g · solid), depending on the type of cationic paper additive used, all cationic groups are electrically May become neutral and may not be fixed to the pulp, resulting in a problem that the paper strength enhancing effect cannot be obtained.
上記の方法で製造されるセルロース解重合物は、カチオン性製紙用添加剤と併用して、抄紙工程で添加することにより、紙に紙力増強効果を付与することができる。これは、パルプは基本的にアニオン性を有しており、同じアニオン性を有する上記セルロース解重合物は、電荷的に反発を生じてパルプへの定着性は悪いが、上記カチオン性製紙用添加剤を用いることにより、上記セルロース解重合物は、カチオン性製紙用添加剤とイオンコンプレックスを形成することができ、パルプへの定着性を向上させることが可能となる。 The cellulose depolymerized product produced by the above method can be used in combination with a cationic papermaking additive and added in the papermaking process to impart a paper strength enhancing effect to the paper. This is because the pulp basically has anionic property, and the cellulose depolymerized product having the same anionic property is repelled in charge and has poor fixability to the pulp, but the cationic papermaking additive is used. By using an agent, the cellulose depolymerized product can form an ion complex with a cationic papermaking additive, and the fixability to pulp can be improved.
このカチオン性製紙用添加剤とは、一般的に製紙用添加剤として使用されるカチオン基を有する樹脂もしくは多糖類をいう。このカチオン性製紙用添加剤の具体例としては、アクリルアミド重合物をカチオン変性したもの、ジアルキルアミノエチル（メタ）アクリレートの単独重合体又は共重合体、ポリエチレンイミン、ジアリルアミンやトリメチルアンモニウムクロライド等のアンモニウム塩をポリマーに反応させたカチオン性第三級アンモニウム塩、カチオン性第４級アンモニウム塩、それらの両性ポリマー、カチオン化澱粉、両性澱粉等が挙げられる。 The cationic papermaking additive refers to a resin or polysaccharide having a cationic group generally used as a papermaking additive. Specific examples of this cationic papermaking additive include cation polymer-modified acrylamide polymers, homopolymers or copolymers of dialkylaminoethyl (meth) acrylate, ammonium salts such as polyethyleneimine, diallylamine and trimethylammonium chloride. And cationic tertiary ammonium salts, cationic quaternary ammonium salts, amphoteric polymers thereof, cationized starches, and amphoteric starches.
具体的な製紙方法としては、パルプスラリーに、上記セルロース解重合物及びカチオン性製紙用添加剤を添加して、これを抄紙する方法が挙げられる。上記のセルロース解重合物やカチオン性製紙用添加剤を、パルプスラリーへ添加する順序は、特に限定されるものではない。また、これらの添加方法は特に限定されず、また、工業用水等によって希釈して添加してもよく、そのまま添加してもよい。 As a specific papermaking method, a method of making a paper by adding the cellulose depolymerized product and the cationic papermaking additive to the pulp slurry can be mentioned. The order in which the cellulose depolymerized product and the cationic papermaking additive are added to the pulp slurry is not particularly limited. Moreover, these addition methods are not specifically limited, Furthermore, you may dilute with industrial water etc. and may add as it is.
カチオン性製紙用添加剤に対する上記のセルロース解重合物の使用割合は、重量比（セルロース解重合物からなる製紙用添加剤：カチオン性製紙用添加剤）で、１：１０以上がよく、１：４以上が好ましい。１：１０よりセルロース解重合物が少ないと、カチオン性製紙用添加剤の添加量に対してセルロース解重合物の添加量が少ないため、セルロース解重合物による十分な紙力増強効果が得られないという問題点を生じる場合がある。一方、セルロース解重合物の使用割合の上限は、１０：１がよく、４：１が好ましい。１０：１よりセルロース解重合物が多いと、添加量に対してパルプへの定着量が少なく、添加量に見合う十分な紙力増強効果が得られないという問題点を生じる場合がある。 The use ratio of the above cellulose depolymerized product to the cationic papermaking additive is preferably a weight ratio (papermaking additive made of cellulose depolymerized product: cationic papermaking additive) of 1:10 or more. 4 or more is preferable. When the amount of cellulose depolymerized product is less than 1:10, the amount of cellulose depolymerized product added is small relative to the amount of cationic papermaking additive added, so that sufficient paper strength enhancement effect by cellulose depolymerized product cannot be obtained. May cause problems. On the other hand, the upper limit of the use ratio of the cellulose depolymerized product is preferably 10: 1 and is preferably 4: 1. When the cellulose depolymerized product is more than 10: 1, the amount of fixing to the pulp is small with respect to the added amount, and there may be a problem that a sufficient paper strength enhancing effect corresponding to the added amount cannot be obtained.
上記セルロース解重合物のパルプに対する添加量は、パルプ固形分に対し、固形分で０．０１重量％以上がよく、０．０３重量％以上が好ましい。０．０１重量％より少ないと、パルプに定着するセルロース解重合物の量が少なく、紙力増強効果が十分に得られないという問題点を生じる場合がある。一方、添加量の上限は、３重量％がよく、１重量％が好ましい。３重量％より多いと、添加したセルロース解重合物の大部分がパルプに定着せず、添加量に見合う十分な紙力増強効果が得られないという問題点を生じる場合がある。 The amount of the cellulose depolymerized product added to the pulp is preferably 0.01% by weight or more, and preferably 0.03% by weight or more, based on the solid content of the pulp. If it is less than 0.01% by weight, the amount of cellulose depolymerized product fixed on the pulp is small, and there may be a problem that the paper strength enhancing effect cannot be obtained sufficiently. On the other hand, the upper limit of the addition amount is preferably 3% by weight, and preferably 1% by weight. If it is more than 3% by weight, most of the added cellulose depolymerized product will not be fixed to the pulp, and there may be a problem that a sufficient paper strength enhancing effect corresponding to the added amount cannot be obtained.
上記セルロース解重合物は、上記以外の紙力増強効果のあるカチオン性製紙用添加剤や、紙力増強効果のないカチオン性製紙用添加剤と共に添加してもよい。上記セルロース解重合物を上記以外の紙力増強効果のあるカチオン性製紙用添加剤と共に添加した場合、添加したカチオン性製紙用添加剤による紙力増強効果に加え、さらなる紙力増強効果が得られる。また、上記セルロース解重合物を上記以外の紙力増強効果のないカチオン性製紙用添加剤と共に添加した場合、上記セルロース解重合物を添加することにより紙力増強効果が得られる。 The cellulose depolymerized product may be added together with a cationic papermaking additive having a paper strength enhancing effect other than the above and a cationic papermaking additive having no paper strength enhancing effect. When the above cellulose depolymerized product is added together with a cationic papermaking additive having a paper strength enhancing effect other than the above, a paper strength enhancing effect can be obtained in addition to the paper strength enhancing effect of the added cationic papermaking additive. . Further, when the cellulose depolymerized product is added together with a cationic papermaking additive having no other paper strength enhancing effect than the above, a paper strength enhancing effect can be obtained by adding the cellulose depolymerized product.
以下、この発明についての具体例を挙げて説明する。なお、この発明は、下記の具体例の範囲に制限されるものではない。まず、評価方法について説明する。 Hereinafter, specific examples of the present invention will be described. In addition, this invention is not restrict | limited to the range of the following specific example. First, the evaluation method will be described.
＜評価方法＞
［重量平均分子量］
下記に示す条件下で、ゲル浸透クロマトグラフィー（ＧＰＣ）によって重量平均分子量を測定した。
測定対象の解重合物は、下記の溶離液を加えて固形分濃度を０．２％に調整した。
・装置…ＴＯＳＯＨ（株）製：ＨＬＣ−８２２０ＧＰＣ
・カラム…ＴＯＳＯＨ ＴＳＫ−ＧＥＬ ＳＵＰＥＲ ＡＷ−Ｈ、
・標準物質…プルラン
・溶離液…ＤＭＳＯ（５ｍＭ−ＮａＮＯ３）
<Evaluation method>
[Weight average molecular weight]
The weight average molecular weight was measured by gel permeation chromatography (GPC) under the conditions shown below.
The depolymerized product to be measured was adjusted to a solid content concentration of 0.2% by adding the following eluent.
・ Device: TOSOH Co., Ltd .: HLC-8220GPC
Column: TOSOH TSK-GEL SUPER AW-H
Reference material: Pullulan Eluent: DMSO (5 mM NaNO 3 )
［硫黄含有率］
三菱化学（株）製の微量硫黄計ＴＮＳＸ ＴＯＸ−１００型を用いて、標準物質にＤＭＳＯを使用し、測定対象の解重合物の硫黄含有率を測定した。
[Sulfur content]
Using a micro sulfur meter TNSX TOX-100 type manufactured by Mitsubishi Chemical Corporation, DMSO was used as a standard substance, and the sulfur content of the depolymerized product to be measured was measured.
［負電荷量］
ｍｕｅｔｅｋ社製ＰＣＤ０３を用いて、測定対象の解重合物の水溶液１０ｍＬをセルに入れ、１／４００Ｎポリ（塩化ジアリルジメチルアンモニウム）溶液（ＤＡＤＭＡＣ）で等電点まで滴定を行った。滴定量と固形分から１ｇ当たりの負電荷量を求めた。
[Negative charge]
Using PCD03 manufactured by mutek, 10 mL of an aqueous solution of a depolymerized product to be measured was placed in a cell, and titration was performed with a 1 / 400N poly (diallyldimethylammonium chloride) solution (DADMAC) to the isoelectric point. The amount of negative charge per gram was determined from the titration amount and the solid content.
［スルホン酸基の置換度算出方法］
ＧＰＣにより測定した平均分子量をもつ解重合物１分子中に１つのスルホン酸基が置換されている場合を置換度１とし、測定した平均分子量と硫黄含有率よりスルホン酸基の置換度を以下の式（１）で算出した。
[Calculation method of substitution degree of sulfonic acid group]
When one sulfonic acid group is substituted in one molecule of the depolymerized product having an average molecular weight measured by GPC, the substitution degree is 1, and the substitution degree of the sulfonic acid group is determined from the measured average molecular weight and sulfur content as follows: It calculated by Formula (1).
［比圧縮強度］
ＪＩＳ Ｐ８１２６にしたがって測定した。
[Specific compression strength]
It measured according to JIS P8126.
［裂断長］
ＪＩＳ Ｐ８１１６にしたがって測定した。
[Cut length]
It measured according to JIS P8116.
（実施例１）
結晶性セルロース（ＭＥＲＣＫ社製：アビセル）１０ｇを用い、これと８０重量％硫酸水溶液２０ｇとを、１０℃で撹拌しながら２時間加水分解して、セルロースの解重合物（平均分子量１０８６８）の酸水溶液を得た。この酸水溶液に水酸化カルシウムを添加して硫酸を中和後、析出した硫酸カルシウムを除去し、得られたセルロース解重合物の水溶液を凍結乾燥して、セルロース解重合物９．４ｇ（収率９４％）を得た。得られたセルロース解重合物の硫黄含有率は４．９％であり、平均分子量と硫黄含有率より算出したスルホン酸基の置換度は１６．６となった。また、負電荷量は−１．０ｍｅｑ／ｇ・ｓｏｌｉｄであった。
Example 1
10 g of crystalline cellulose (MERCK: Avicel) was used and hydrolyzed with 20 g of 80% by weight sulfuric acid aqueous solution for 2 hours with stirring at 10 ° C. to obtain an acid of cellulose depolymerized product (average molecular weight 10868). An aqueous solution was obtained. Calcium hydroxide was added to this acid aqueous solution to neutralize the sulfuric acid, the precipitated calcium sulfate was removed, and the resulting cellulose depolymerized aqueous solution was lyophilized to obtain 9.4 g of cellulose depolymerized product (yield 94%). The obtained cellulose depolymerized product had a sulfur content of 4.9%, and the substitution degree of the sulfonic acid group calculated from the average molecular weight and the sulfur content was 16.6. The negative charge amount was −1.0 meq / g · solid.
（実施例２）
セルロースを主成分とするバイオマス原料として段ボール古紙（セルロース含有率７０％）１０ｇを用い、これと８０重量％硫酸水溶液１５ｇとを、１０℃で撹拌しながら２時間加水分解して、セルロースの解重合物（平均分子量２２７８４）の酸水溶液を得た。加水分解反応後の溶液には不溶の残渣が分散しており、ペースト状に近い溶液となった。この酸水溶液に水を添加してセルロース解重合物を溶解、残渣を分散させた後に、水酸化カルシウムを添加して硫酸を中和後、析出した硫酸カルシウムと残渣を除去し、得られたセルロース解重合物の水溶液を凍結乾燥して、セルロース解重合物６．７ｇ（収率９６％ 対段ボール古紙中含有セルロース分）を得た。得られたセルロース解重合物の硫黄含有率は１．８％であり、平均分子量と硫黄含有率より算出したスルホン酸基の置換度は１２．８となった。また、負電荷量は−１．１ｍｅｑ／ｇ・ｓｏｌｉｄであった。
(Example 2)
Cellulose waste paper (cellulose content 70%) 10g is used as a biomass raw material mainly composed of cellulose, and 80g% sulfuric acid aqueous solution 15g is hydrolyzed for 2 hours with stirring at 10 ° C to depolymerize cellulose. Acid solution (average molecular weight 22784) was obtained. Insoluble residues were dispersed in the solution after the hydrolysis reaction, and the solution became a paste-like solution. After adding water to this acid aqueous solution to dissolve the cellulose depolymerized product, dispersing the residue, adding calcium hydroxide to neutralize the sulfuric acid, removing the precipitated calcium sulfate and the residue, and obtaining the cellulose The aqueous solution of the depolymerized product was lyophilized to obtain 6.7 g of cellulose depolymerized product (yield 96% vs. cellulose content in the corrugated cardboard). The obtained cellulose depolymerized product had a sulfur content of 1.8%, and the degree of substitution of the sulfonic acid group calculated from the average molecular weight and the sulfur content was 12.8. Further, the negative charge amount was −1.1 meq / g · solid.
（実施例３）
セルロースを主成分とするバイオマス原料として稲わら（セルロース含有率６０％）１０ｇを用い、これと８０重量％硫酸水溶液２０ｇとを、１０℃で撹拌しながら１時間３０分間加水分解して、セルロースの解重合物（平均分子量１９００１）の酸水溶液を得た。加水分解反応後の溶液には不溶の残渣が分散しており、ペースト状に近い溶液となった。この酸水溶液に水を添加してセルロース解重合物を溶解、残渣を分散させた後に、水酸化カルシウムを添加して硫酸を中和後、析出した硫酸カルシウムと残渣を除去し、得られたセルロース解重合物の水溶液を凍結乾燥して、セルロース解重合物５．４ｇ（収率９０％ 対稲わら中含有セルロース分）を得た。得られたセルロース解重合物の硫黄含有率は１．６％であり、平均分子量と硫黄含有率より算出したスルホン酸基の置換度は９．５となった。また、負電荷量は−１．１ｍｅｑ／ｇ・ｓｏｌｉｄであった。
(Example 3)
10 g of rice straw (cellulose content: 60%) is used as a biomass raw material mainly composed of cellulose, and 20 g of 80 wt% sulfuric acid aqueous solution is hydrolyzed for 1 hour and 30 minutes with stirring at 10 ° C. An acid aqueous solution of a depolymerized product (average molecular weight 19001) was obtained. Insoluble residues were dispersed in the solution after the hydrolysis reaction, and the solution became a paste-like solution. After adding water to this acid aqueous solution to dissolve the cellulose depolymerized product, dispersing the residue, adding calcium hydroxide to neutralize the sulfuric acid, removing the precipitated calcium sulfate and the residue, and obtaining the cellulose The aqueous solution of the depolymerized product was lyophilized to obtain 5.4 g of cellulose depolymerized product (yield 90% of cellulose contained in rice straw). The obtained cellulose depolymerized product had a sulfur content of 1.6%, and the degree of substitution of the sulfonic acid group calculated from the average molecular weight and the sulfur content was 9.5. Further, the negative charge amount was −1.1 meq / g · solid.
（実施例４）
セルロースを主成分とするバイオマス原料として製紙スラッジ（セルロース含有率４０％）１０ｇを用い、これと８０重量％硫酸水溶液２０ｇとを、１０℃で撹拌しながら２時間加水分解して、セルロースの解重合物（平均分子量１６２４２）の酸水溶液を得た。加水分解反応後の溶液には不溶の残渣が分散しており、ペースト状に近い溶液となった。この酸水溶液に水を添加してセルロース解重合物を溶解、残渣を分散させた後に、水酸化カルシウムを添加して硫酸を中和後、析出した硫酸カルシウムと残渣を除去し、得られたセルロース解重合物の水溶液を凍結乾燥して、セルロース解重合物３．７ｇ（収率９３％ 対製紙スラッジ中含有セルロース分）を得た。得られたセルロース解重合物の硫黄含有率は１．９％であり、平均分子量と硫黄含有率より算出したスルホン酸基の置換度は９．６となった。また、負電荷量は−０．９９ｍｅｑ／ｇ・ｓｏｌｉｄであった。
Example 4
10 g of paper sludge (cellulose content 40%) is used as a biomass raw material mainly composed of cellulose, and 20 g of 80 wt% sulfuric acid aqueous solution is hydrolyzed at 10 ° C. for 2 hours to depolymerize cellulose. An acid aqueous solution of the product (average molecular weight 16242) was obtained. Insoluble residues were dispersed in the solution after the hydrolysis reaction, and the solution became a paste-like solution. After adding water to this acid aqueous solution to dissolve the cellulose depolymerized product, dispersing the residue, adding calcium hydroxide to neutralize the sulfuric acid, removing the precipitated calcium sulfate and the residue, and obtaining the cellulose The aqueous solution of the depolymerized product was freeze-dried to obtain 3.7 g of cellulose depolymerized product (yield 93% with respect to cellulose contained in paper sludge). The obtained cellulose depolymerized product had a sulfur content of 1.9%, and the degree of substitution of the sulfonic acid group calculated from the average molecular weight and the sulfur content was 9.6. Further, the negative charge amount was −0.99 meq / g · solid.
（比較例１）
セルロースを主成分とするバイオマス原料として段ボール古紙（セルロース含有率７０％）１０ｇを用い、これと８０重量％硫酸水溶液２０ｇとを、４０℃で撹拌しながら３０分間加水分解して、セルロースの解重合物（平均分子量１３２８）の酸水溶液を得た。加水分解反応後の溶液には不溶の残渣が分散しており、ペースト状に近い溶液となった。この酸水溶液に水を添加してセルロース解重合物を溶解、残渣を分散させた後に、水酸化カルシウムを添加して硫酸を中和後、析出した硫酸カルシウムと残渣を除去し、得られたセルロース解重合物の水溶液を凍結乾燥して、セルロース解重合物６．６ｇ（収率９４％ 対段ボール古紙中含有セルロース分）を得た。得られたセルロース解重合物の硫黄含有率は２．７％であり、平均分子量と硫黄含有率より算出したスルホン酸基の置換度は１．１となった。また、負電荷量は−０．２１ｍｅｑ／ｇ・ｓｏｌｉｄであった。
(Comparative Example 1)
Cellulose waste paper (cellulose content 70%) 10g is used as a biomass raw material mainly composed of cellulose, and this is hydrolyzed with 20g of 80wt% sulfuric acid aqueous solution at 40 ° C for 30 minutes to depolymerize cellulose. An acid aqueous solution of the product (average molecular weight 1328) was obtained. Insoluble residues were dispersed in the solution after the hydrolysis reaction, and the solution became a paste-like solution. After adding water to this acid aqueous solution to dissolve the cellulose depolymerized product, dispersing the residue, adding calcium hydroxide to neutralize the sulfuric acid, removing the precipitated calcium sulfate and the residue, and obtaining the cellulose The aqueous solution of the depolymerized product was freeze-dried to obtain 6.6 g of cellulose depolymerized product (yield 94% vs. cellulose content in the corrugated cardboard). The obtained cellulose depolymerized product had a sulfur content of 2.7%, and the degree of substitution of the sulfonic acid group calculated from the average molecular weight and the sulfur content was 1.1. The negative charge amount was −0.21 meq / g · solid.
（比較例２）
コーンスターチ（日本コーンスターチ（株）製：含有水分率１２．５％）１１．４ｇを用い、これと８０重量％硫酸水溶液２０ｇとを、１０℃で撹拌しながら２時間加水分解して、澱粉の解重合物（平均分子量１４２４５）の酸水溶液を得た。この酸水溶液に水酸化カルシウムを添加して硫酸を中和後、析出した硫酸カルシウムを除去し、得られた澱粉解重合物の水溶液を凍結乾燥して、澱粉解重合物９．６ｇ（収率９６％）を得た。得られた澱粉解重合物の硫黄含有率は１．９％であり、平均分子量と硫黄含有率より算出したスルホン酸基の置換度は８．５となった。また、負電荷量は−０．８９ｍｅｑ／ｇ・ｓｏｌｉｄであった。
(Comparative Example 2)
By using 11.4 g of corn starch (manufactured by Nippon Corn Starch Co., Ltd .: moisture content 12.5%) and 20 g of 80% by weight sulfuric acid aqueous solution at 10 ° C. with stirring for 2 hours, An acid aqueous solution of a polymer (average molecular weight 14245) was obtained. Calcium hydroxide was added to the acid aqueous solution to neutralize the sulfuric acid, the precipitated calcium sulfate was removed, and the resulting starch depolymerized aqueous solution was lyophilized to obtain 9.6 g of starch depolymerized product (yield) 96%). The obtained starch depolymerized product had a sulfur content of 1.9%, and the degree of substitution of the sulfonic acid group calculated from the average molecular weight and the sulfur content was 8.5. Further, the negative charge amount was −0.89 meq / g · solid.
（実施例５〜７、比較例３〜６）
濃度５．０％の古紙パルプスラリーに、水を添加して濃度１．０％の古紙パルプスラリーを調製した。（カナディアン・スタンダード・フリーネス（ＣＳＦ）約５３０）パルプ固形分に対し、各薬剤の固形分換算で硫酸バンド、セルロースもしくは澱粉解重合物（１％水溶液）、レンゴー（株）製：両性ポリアクリルアミド系紙力剤（ＰＡＭ）もしくは糊化したカチオン化澱粉（ジー・エス・エル・ジャパン（株）製：ＣａＳｔａｒｃｈ Ｈ）を表１に記載の添加率で添加し、４００ｒｐｍで撹拌下、硫酸バンド（１分撹拌）→セルロースもしくは澱粉解重合物（１分撹拌）→ＰＡＭもしくはカチオン化澱粉（４分撹拌）の順序で添加した。
このパルプスラリーをＪＩＳ Ｐ８２２２にしたがってシートマシンにて抄紙して、湿紙を得た。この湿紙を、プレス後、ドラムドライヤーで乾燥して１６０ｇ／ｍ２の手抄き紙を得た。得られた手抄き紙を２３℃、５０％ＲＨの条件下で２４時間調湿した後、上記の方法で各評価を行った。その結果を表２に示す。
(Examples 5-7, Comparative Examples 3-6)
Water was added to a used paper pulp slurry having a concentration of 5.0% to prepare a used paper pulp slurry having a concentration of 1.0%. (Canadian Standard Freeness (CSF) approx. 530) For pulp solids, sulfate band, cellulose or starch depolymerized product (1% aqueous solution), Rengo Co., Ltd .: Amphoteric polyacrylamide A paper strength agent (PAM) or gelatinized cationized starch (manufactured by GS Japan Co., Ltd .: CaStarch H) was added at the addition rate shown in Table 1, and the sulfuric acid band (1 Minutes stirring) → cellulose or starch depolymerized product (1 minute stirring) → PAM or cationized starch (4 minutes stirring).
The pulp slurry was made with a sheet machine according to JIS P8222 to obtain wet paper. This wet paper was pressed and then dried with a drum dryer to obtain 160 g / m 2 of handmade paper. The obtained handmade paper was conditioned for 24 hours under conditions of 23 ° C. and 50% RH, and then each evaluation was performed by the above methods. The results are shown in Table 2.
（実施例８〜９、比較例７〜８）
ＮＵＫＰ（含水率約１２％）をＪＩＳ Ｐ８２２０にしたがって標準離解し、濃度１．０％のパルプスラリーを調製した。そのパルプスラリーを２００ｍＬずつ分取し、パルプ固形分に対し、各薬剤の固形分換算で硫酸バンド０．７％、セルロースもしくは澱粉解重合物（１％水溶液）０．１％、レンゴー（株） 製：両性ポリアクリルアミド系紙力剤（ＰＡＭ）０．１％を６００ｒｐｍで撹拌下、硫酸バンド（１分撹拌）→セルロースもしくは澱粉解重合物（１分撹拌）→ＰＡＭ（４分撹拌）の順序で添加した。このパルプスラリーを目開き１６０μｍのふるいでろ過し、パルプを除去した溶液を得た。３０００ｒｐｍ、３ｍｉｎ遠心分離により、微細繊維を除去後、上澄み液をフェノール硫酸法にて糖濃度測定した。得られた糖濃度より、下記の方法によって解重合物の歩留りを算出した。その結果を表３に示す。
(Examples 8-9, Comparative Examples 7-8)
NUKP (moisture content of about 12%) was standardly disaggregated according to JIS P8220 to prepare a pulp slurry having a concentration of 1.0%. Each 200 mL of the pulp slurry was collected, and the pulp solid content was 0.7% sulfate band, 0.1% cellulose or starch depolymerized product (1% aqueous solution), Rengo Co., Ltd. Manufactured: Amphoteric polyacrylamide paper strength agent (PAM) 0.1% with stirring at 600 rpm, sulfuric acid band (1 minute stirring) → cellulose or starch depolymerized product (1 minute stirring) → PAM (4 minutes stirring) Added at. The pulp slurry was filtered through a sieve having an opening of 160 μm to obtain a solution from which the pulp was removed. After removing fine fibers by centrifugation at 3000 rpm for 3 minutes, the supernatant liquid was subjected to sugar concentration measurement by the phenol-sulfuric acid method. From the sugar concentration obtained, the yield of the depolymerized product was calculated by the following method. The results are shown in Table 3.
［歩留り］
硫酸バンド、ＰＡＭのみ添加したサンプルをブランクとし、以下の計算式で解重合物の歩留りを算出した。
・歩留り０％の場合のパルプを除去した溶液中解重合物濃度（ｍｇ／Ｌ）＝解重合物添加量（ｍｇ）／０．２０Ｌ
・歩留り（％）＝1−｛ ( 糖濃度測定値−ブランク糖濃度)／歩留り０％の場合のパルプを除去した溶液中解重合物濃度 ｝
[Yield]
The sample to which only the sulfuric acid band and PAM were added was used as a blank, and the yield of the depolymerized product was calculated using the following formula.
-Depolymerized product concentration (mg / L) in solution from which pulp was removed when the yield was 0% = Depolymerized product added amount (mg) /0.20L
-Yield (%) = 1-{(Measured sugar concentration-blank sugar concentration) / depolymerized solution concentration in solution from which pulp is removed when yield is 0%}
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02251696A (en) * | 1988-10-03 | 1990-10-09 | Hercules Inc | Dry strength-reinforcing agent for paper-making |
| JPH07324221A (en) * | 1994-05-27 | 1995-12-12 | Kimberly Clark Corp | Sulfonated cellulose and its preparation |
| JPH11515063A (en) * | 1995-11-03 | 1999-12-21 | ウェヤーハウザー・カンパニー | Paper and paper-like products containing water-insoluble fibrous carboxyalkyl cellulose |
| JP2002513872A (en) * | 1998-04-30 | 2002-05-14 | メツェーセーラ オーワイジェイ | Manufacturing method of textile products |
| JP2003147691A (en) * | 2001-08-20 | 2003-05-21 | Armstrong World Industries Inc | Binder for fibrous sheet |
| JP2010533799A (en) * | 2007-07-16 | 2010-10-28 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Filler composition |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02251696A (en) * | 1988-10-03 | 1990-10-09 | Hercules Inc | Dry strength-reinforcing agent for paper-making |
| JPH07324221A (en) * | 1994-05-27 | 1995-12-12 | Kimberly Clark Corp | Sulfonated cellulose and its preparation |
| JPH11515063A (en) * | 1995-11-03 | 1999-12-21 | ウェヤーハウザー・カンパニー | Paper and paper-like products containing water-insoluble fibrous carboxyalkyl cellulose |
| JP2002513872A (en) * | 1998-04-30 | 2002-05-14 | メツェーセーラ オーワイジェイ | Manufacturing method of textile products |
| JP2003147691A (en) * | 2001-08-20 | 2003-05-21 | Armstrong World Industries Inc | Binder for fibrous sheet |
| JP2010533799A (en) * | 2007-07-16 | 2010-10-28 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Filler composition |
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