JP4522692B2 - Paper making adhesive - Google Patents

Paper making adhesive Download PDF

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JP4522692B2
JP4522692B2 JP2003398922A JP2003398922A JP4522692B2 JP 4522692 B2 JP4522692 B2 JP 4522692B2 JP 2003398922 A JP2003398922 A JP 2003398922A JP 2003398922 A JP2003398922 A JP 2003398922A JP 4522692 B2 JP4522692 B2 JP 4522692B2
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acrylamide copolymer
mass
acrylamide
papermaking
aqueous solution
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JP2005154978A (en
JP2005154978A5 (en
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孝則 中里
洋二 和田
康治 森
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Dia Nitrix Co Ltd
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Dia Nitrix Co Ltd
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Priority to KR1020040097340A priority patent/KR101123548B1/en
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides

Description

本発明は、ティッシュペーパー、タオル紙、トイレットペーパー等を抄造する際に、紙料繊維に分散性を付与するために使用する抄紙用粘剤に関する。   The present invention relates to a papermaking adhesive used for imparting dispersibility to a stock fiber when making tissue paper, towel paper, toilet paper, and the like.

和紙、ティッシュペーパー、トイレットペーパー、タオル紙等を抄造する際に、紙料の水中での分散性を向上させるために分散粘剤を用いる抄紙法は古くから行われている。この分散粘剤は抄紙用粘剤と呼ばれ、例えば、トロロアオイ根の抽出粘液等の天然物が知られているが、天然物のトロロアオイは、腐敗による変質や品質が安定しないこと、抽出操作が大変なこと、価格が不安定であること等の欠点があり、工業的には現在殆ど使用されていない。
また、分散粘剤としては、合成高分子化合物を使用することもでき、例えば、ポリエチレンオキサイド、アニオン性のアクリルアミド系重合体が使用されている。
ティッシュペーパーやタオル紙を抄造する際には、紙料に湿潤紙力増強剤等のカチオン性高分子化合物が添加されていることが多く、また、柔軟剤、染料、顔料等のカチオン性薬剤が添加されている場合もある。そのため、アニオン性のアクリルアミド系重合体が含まれた抄紙用粘剤を、カチオン性高分子化合物またはカチオン性薬剤を含有した紙料に使用すると、電荷の作用により、紙料繊維が凝集するので抄紙の際の分散が困難になるという問題があった。トイレットペーパーの場合はアニオン性のアクリルアミド系重合体が使用可能であるが、一種類の抄紙用粘剤でティッシュペーパーを併産している場合や、白水が混合する場合にはアニオン性のアクリルアミド系重合体が使用できないという問題があった。 When making Japanese paper, tissue paper, toilet paper, towel paper, and the like, a paper making method using a dispersing adhesive has been practiced for a long time in order to improve the dispersibility of the stock in water. This dispersion viscosity agent is called a papermaking viscosity agent.For example, natural products such as extraction mucilage of troolloi root are known. There are drawbacks such as seriousness and unstable price, and it is hardly used industrially at present.
Moreover, a synthetic polymer compound can also be used as a dispersion viscosity agent, for example, a polyethylene oxide and an anionic acrylamide type polymer are used.
When making tissue paper or towel paper, a cationic polymer compound such as a wet paper strength enhancer is often added to the stock, and a cationic agent such as a softener, dye, or pigment is used. It may be added. For this reason, if a paper-making adhesive containing an anionic acrylamide polymer is used in a stock containing a cationic polymer compound or a cationic agent, the stock fiber aggregates due to the effect of electric charge, so paper making. There is a problem that dispersion during the process becomes difficult. In the case of toilet paper, an anionic acrylamide polymer can be used, but an anionic acrylamide polymer is used when tissue paper is co-produced with one type of papermaking adhesive or when white water is mixed. There was a problem that the polymer could not be used.

そこで、電荷の作用がないノニオン性の抄紙用粘剤が使用されている。具体的なノニオン性抄紙用粘剤としては、例えば、ポリエチレンオキサイド系抄紙用粘剤が挙げられる。現在、ノニオン性抄紙用粘剤としては、殆どの場合ポリエチレンオキサイドが使用されている。
また、ポリエチレンオキサイドと非イオンタイプの高分子ポリアクリルアミドを使用する方法が提案され（例えば、特許文献１参照）、ポリアクリルアミド単独で使用する場合より著しく地合が改善された紙が得られると提案がなされている。
さらに、アクリルアミド単量体単位とＮ−ビニルカルボン酸アミド単量体単位を含む共重合体からなる抄紙用粘剤が提案されている（例えば、特許文献２参照。）。
また、アクリルアミド系ノニオン性（共）重合体と食塩とを含む食塩水溶液の粘度が、前記食塩水溶液と同じ濃度のアクリルアミド系ノニオン性（共）重合体を純水中に含む純水溶液の粘度より高いようなアクリルアミド系ノニオン性（共）重合体を用いることで、加水分解の抑制されたアクリルアミド系ノニオン性（共）重合体を用いて抄紙用粘剤を構成することが提案されている（特許文献３参照。）。
特公昭５２−１５６８１号公報 特開２０００−２９０８９２号公報 特開２００３−２５３５８７号公報 Therefore, nonionic paper-making adhesives that do not have a charge effect are used. Specific examples of nonionic papermaking adhesives include polyethylene oxide papermaking adhesives. At present, in most cases, polyethylene oxide is used as a nonionic papermaking adhesive.
In addition, a method using polyethylene oxide and nonionic polymer polyacrylamide has been proposed (see, for example, Patent Document 1), and it is proposed that a paper whose texture is remarkably improved as compared with the case of using polyacrylamide alone is proposed. Has been made.
Furthermore, a papermaking adhesive made of a copolymer containing an acrylamide monomer unit and an N-vinylcarboxylic acid amide monomer unit has been proposed (see, for example, Patent Document 2).
Further, the viscosity of the saline solution containing the acrylamide nonionic (co) polymer and sodium chloride is higher than the viscosity of the pure aqueous solution containing the acrylamide nonionic (co) polymer having the same concentration as the saline solution in pure water. It has been proposed that an acrylamide-based nonionic (co) polymer with suppressed hydrolysis be used to form a papermaking adhesive using such an acrylamide-based nonionic (co) polymer (Patent Literature). 3).
Japanese Patent Publication No. 52-15681 JP 2000-290892 A JP 2003-255357 A

しかしながら、抄紙用粘剤としてポリエチレンオキサイドを添加すると、溶解条件によりポリエチレンオキサイドが粘度低下を起こすために、安定に抄紙するのが容易ではないこと、高価であること等の問題点を有していた。さらに、抄紙工程中に発泡するため、発泡を抑える消泡剤を多量に添加しなければならなかった。
特許文献１に記載の発明では、ポリエチレンオキサイドの発泡は低減されているが、ティッシュペーパーやタオル紙のようにカチオン性高分子化合物やカチオン性薬剤が含まれている抄造ではポリエチレンオキサイド単独に比べて十分に均一な地合が得られるものではなかった。
特許文献２に記載の発明では、Ｎ−ビニルカルボン酸アミドが高価であったり、安定した品質のＮ−ビニルカルボン酸アミドを得るのが困難である問題点があった。また、ポリエチレンオキサイドに比較して紙料繊維の凝集が若干強い傾向があり、抄紙性能的には十分ではなかった。
特許文献３に記載の抄紙用粘剤は溶解速度が遅く溶解に長時間を要し、溶解が不十分な時点で使用すると、未溶解物により抄紙トラブルが発生する等の問題点があった。
さらにポリエチレンオキサイド系の抄紙用粘剤に比べてポリアクリルアミド系抄紙用粘剤は溶解速度が遅いため、ポリエチレンオキサイドとポリアクリルアミド系抄紙用粘剤とを混合使用する場合、ポリエチレンオキサイド単独の場合より、撹拌時間を延長する必要がある。ポリエチレンオキサイドを含む水溶液の撹拌力を強化したり、撹拌時間を延長すると、ポリエチレンオキサイド部分に撹拌による剪断力が必要以上に加わるため粘度低下を招く問題点があり、溶解条件の設定が難しいという欠点があった。 However, when polyethylene oxide is added as a papermaking viscosity agent, the viscosity of polyethylene oxide decreases depending on the dissolution conditions, so there are problems such as being not easy to make paper stably and being expensive. . Furthermore, since foaming occurs during the paper making process, a large amount of an antifoaming agent that suppresses foaming has to be added.
In the invention described in Patent Document 1, foaming of polyethylene oxide is reduced, but in papermaking containing a cationic polymer compound or a cationic drug such as tissue paper or towel paper, compared to polyethylene oxide alone. A sufficiently uniform formation was not obtained.
In the invention described in Patent Document 2, there is a problem that N-vinylcarboxylic amide is expensive or it is difficult to obtain a stable quality N-vinylcarboxylic amide. Further, the aggregation of the stock fibers tended to be slightly stronger than that of polyethylene oxide, and the papermaking performance was not sufficient.
The papermaking adhesive described in Patent Document 3 has a problem that the dissolution rate is slow and a long time is required for dissolution, and if it is used at a time when the dissolution is insufficient, a papermaking trouble occurs due to undissolved material.
Furthermore, since the dissolution rate of polyacrylamide papermaking adhesive is slower than that of polyethyleneoxide papermaking adhesive, when polyethylene oxide and polyacrylamide papermaking adhesive are mixed and used, than the case of polyethylene oxide alone, It is necessary to extend the stirring time. When the stirring force of an aqueous solution containing polyethylene oxide is strengthened or the stirring time is extended, there is a problem that the shearing force due to stirring is added to the polyethylene oxide part more than necessary, leading to a decrease in viscosity, and it is difficult to set dissolution conditions was there.

本発明は上記事情に鑑みてなされたもので、例えば、ティッシュペーパー、タオル紙等の抄紙において、カチオン性高分子またはカチオン性薬剤が添加されていても紙料繊維に分散性を付与することが可能で、抄紙の安定性、製造効率を向上させることが可能な、安価で高性能、かつ取り扱いの容易な抄紙用粘剤を提供することを目的とする。   The present invention has been made in view of the above circumstances. For example, in papermaking such as tissue paper and towel paper, dispersibility can be imparted to the stock fiber even when a cationic polymer or a cationic agent is added. An object of the present invention is to provide an inexpensive, high-performance, and easy-to-handle papermaking adhesive that can improve the stability and production efficiency of papermaking.

本発明者らは、上記課題を解決するために種々検討した結果、アクリルアミドに、ごく少量のアニオン性単量体を共重合する事により、溶解速度の飛躍的に向上したアクリルアミド系共重合体が得られ、しかも、このアクリルアミド系共重合体を用いてカチオン性高分子またはカチオン性薬剤と併用されても紙料繊維の凝集を発生させない抄紙用粘剤を作り得ること、凝集の程度は食塩水溶液の粘度と純水溶液の粘度の数値と関係していることを見出し本発明を完成した。
即ち、本発明の抄紙用粘剤は、アクリルアミドに少なくともアニオン性基を有するビニル系単量体が共重合したアクリルアミド系共重合体を含み、前記アクリルアミド系共重合体が下記粘度条件を満たすことを特徴とする。
（粘度条件）
アクリルアミド系共重合体と食塩４質量％とを含む食塩水溶液の粘度が、前記食塩水溶液と同じ濃度のアクリルアミド系共重合体の純水溶液の粘度より高いこと。
ここで、前記アクリルアミド系共重合体が前記ビニル系単量体単位を０．１〜１．５モル％含有することが好ましい。
前記ビニル系単量体は、アクリル酸（塩）及び／又はアクリルアミド−２−メチルプロパンスルホン酸（塩）であることが好ましい。
前記アクリルアミド系共重合体１質量％を純水中に含む１質量％純水溶液の粘度が２０００ｍＰａ・ｓ以上であることが好ましい。
また、本発明の抄紙用粘剤は、さらにポリエチレンオキサイドを含有し、前記アクリルアミド系共重合体が２０〜７５質量％、ポリエチレンオキサイドが２５〜８０質量％であることが好ましい。 As a result of various investigations to solve the above problems, the present inventors have found that an acrylamide copolymer having a dramatically improved dissolution rate can be obtained by copolymerizing a very small amount of anionic monomer with acrylamide. In addition, this acrylamide copolymer can be used to produce a papermaking adhesive that does not cause aggregation of paper fibers even when used in combination with a cationic polymer or a cationic agent. And the present invention was completed.
That is, the papermaking adhesive of the present invention includes an acrylamide copolymer in which at least a vinyl monomer having an anionic group is copolymerized with acrylamide, and the acrylamide copolymer satisfies the following viscosity condition. Features.
(Viscosity condition)
The viscosity of a saline solution containing an acrylamide copolymer and 4% by mass of sodium chloride is higher than the viscosity of a pure aqueous solution of an acrylamide copolymer having the same concentration as the saline solution.
Here, it is preferable that the acrylamide copolymer having 0.1 to 1.5 mol% including the vinyl monomer units.
The vinyl monomer is preferably acrylic acid (salt) and / or acrylamido-2-methylpropanesulfonic acid (salt).
The viscosity of a 1% by mass pure aqueous solution containing 1% by mass of the acrylamide copolymer in pure water is preferably 2000 mPa · s or more.
Moreover, it is preferable that the adhesive for papermaking of this invention contains a polyethylene oxide further, the said acrylamide type copolymer is 20-75 mass%, and a polyethylene oxide is 25-80 mass%.

本発明の抄紙用粘剤は、ティッシュペーパーやタオル紙等の抄紙において、カチオン性高分子やカチオン性薬剤が添加されていても、紙料繊維に特開２００３−２５３５８７号公報で述べられているノニオン性抄紙用粘剤と同等以上の分散性を付与することや、抄紙の安定性、製造効率を向上させることができ、かつ、溶解速度の飛躍的に向上したものである。溶解速度の向上により、使用の際の不溶解分によるトラブルを減少させると共に、溶解時間を短縮することができる。
さらに、本発明の抄紙用粘剤においてポリエチレンオキサイドを含有させた場合、劣化を最小限にとどめることができ、しかも紙料を分散させる性能を向上させることができる。 The papermaking adhesive of the present invention is described in Japanese Patent Application Laid-Open No. 2003-253587 as a paper fiber even when a cationic polymer or a cationic agent is added to tissue paper or towel paper. It is possible to impart dispersibility equivalent to or higher than that of the nonionic papermaking adhesive, improve the stability and production efficiency of papermaking, and dramatically improve the dissolution rate. By improving the dissolution rate, troubles due to insoluble components during use can be reduced, and the dissolution time can be shortened.
Furthermore, when polyethylene oxide is contained in the papermaking adhesive of the present invention, the deterioration can be minimized, and the performance of dispersing the paper stock can be improved.

以下、本発明について詳しく説明する。
本発明の抄紙用粘剤は、水溶性であるアクリルアミド系共重合体を含む。
アクリルアミド系共重合体としては、該アクリルアミド系共重合体と食塩４質量％とを含む食塩水溶液の粘度が、前記食塩水溶液と同じ濃度のアクリルアミド系共重合体を純水中に含む純水溶液の粘度より高いものが用いられる。
例えば、アクリルアミド系共重合体１質量％と食塩４質量％とを含む１質量％食塩水溶液の粘度が、アクリルアミド系共重合体１質量％を純水中に含む１質量％純水溶液の粘度より１００ｍＰａ・ｓ以上高いアクリルアミド系共重合体を用いることができる。
なお、本発明における「粘度」とは、４質量％食塩水または純水にアクリルアミド系共重合体を添加、３時間撹拌し、得られた溶液を測定温度２５℃にてＢ型粘度計（ローター；Ｎｏ．２、回転数６ｒｐｍ）を使用して測定した値である。 The present invention will be described in detail below.
The papermaking adhesive of the present invention contains a water-soluble acrylamide copolymer.
As the acrylamide copolymer, the viscosity of a saline solution containing the acrylamide copolymer and 4% by mass of sodium chloride is the viscosity of a pure aqueous solution containing an acrylamide copolymer in pure water having the same concentration as the saline solution. Higher ones are used.
For example, the viscosity of a 1% by mass saline solution containing 1% by mass of an acrylamide copolymer and 4% by mass of sodium chloride is 100 mPa than the viscosity of a 1% by mass pure aqueous solution containing 1% by mass of an acrylamide copolymer in pure water. -An acrylamide-type copolymer higher than s can be used.
The “viscosity” in the present invention refers to the addition of an acrylamide copolymer to 4% by mass saline or pure water, and the mixture is stirred for 3 hours. No. 2 and a rotation number of 6 rpm).

上述したようにアクリルアミド系共重合体の食塩水溶液および純水溶液の粘度を測定することにより、以下の理由から、アクリルアミド系共重合体のアニオン性基含有量の程度を知ることができ、アクリルアミド系共重合体がカチオン成分と凝集して紙料の凝集を引き起こす傾向の目安を得ることができる。
すなわち、アクリルアミド系共重合体がカルボキシル基等のアニオン性基を有する場合、このようなアクリルアミド系共重合体を純水に溶解させると、アニオン性基の分子内静電反発によってアクリルアミド系共重合体分子が伸長し、水溶液中での分子の広がりが大きくなり、液の粘度が上昇する。一方、食塩水のような電解質溶液に溶解させた場合、分子内のアニオン性基の分子内静電反発が抑えられるため、分子の伸長による液粘度の上昇は抑えられる。
それに対し、アクリルアミド系共重合体がイオン性の基を含まない場合は、もともと純水中での静電反発が起こらず、純水に溶解したときの粘度上昇も起こらない。
アクリルアミド系共重合体に含まれるアニオン性基が多いほど、静電反発も大きくなり、純水中での粘度上昇も大きくなる。 As described above, by measuring the viscosity of the saline solution and the pure solution of the acrylamide copolymer, the degree of anionic group content of the acrylamide copolymer can be known for the following reasons. A measure of the tendency of the polymer to agglomerate with the cationic component to cause agglomeration of the stock can be obtained.
That is, when the acrylamide copolymer has an anionic group such as a carboxyl group, when such an acrylamide copolymer is dissolved in pure water, the acrylamide copolymer is generated by intramolecular electrostatic repulsion of the anionic group. The molecules are elongated, the spread of the molecules in the aqueous solution is increased, and the viscosity of the liquid is increased. On the other hand, when dissolved in an electrolyte solution such as saline, the intramolecular electrostatic repulsion of the anionic group in the molecule can be suppressed, so that an increase in liquid viscosity due to molecular extension can be suppressed.
On the other hand, when the acrylamide copolymer does not contain an ionic group, electrostatic repulsion does not occur in pure water, and viscosity does not increase when dissolved in pure water.
The more anionic groups contained in the acrylamide copolymer, the greater the electrostatic repulsion and the greater the viscosity increase in pure water.

一般に、抄紙用粘剤に用いられるアクリルアミド系共重合体は、カチオン性物質との反応を防ぐ点ではアニオン性基を有しないことが好ましいが、一方で純ノニオン性の場合、溶解速度が遅くなる傾向にある。
本発明者らは、この二律背反を満たす条件を検討したところ、アクリルアミド系共重合体の溶解性はごく少量のイオン性基を含有させることにより急速に改善されるのに対し、ある限定された量のアニオン性基であれば実際の抄紙系において急速な凝集を引き起こさないこと、及びその凝集の程度は上記の食塩水溶液の粘度と純水中の粘度の数値と関係していることを見出した。即ちアクリルアミド系共重合体について前記食塩水溶液の粘度と前記純水溶液の粘度を比較したときに、前記食塩水溶液の粘度が高い場合は、激しく紙料の凝集を引き起こさない。
前記食塩水溶液の粘度が、前記純水溶液の粘度より高いアクリルアミド系共重合体は、具体的には、アクリルアミド系共重合体がアニオン性基を有するビニル系単量体単位を０．１〜１．５モル％含有するものとして得ることができる。
アニオン性基を有するビニル系単量体が０．１モル％未満であると、抄紙用粘剤の溶解速度改善の効果が小さく、１．５モル％を超えると純水溶液の粘度が高くなり、且つ実際の使用例において紙料の凝集を引き起こす。前記ビニル系単量体は、さらに望ましくは１．０モル％以下である。 In general, an acrylamide copolymer used for a papermaking adhesive preferably has no anionic group in terms of preventing reaction with a cationic substance. On the other hand, in the case of pure nonionicity, the dissolution rate is slow. There is a tendency.
The present inventors examined conditions satisfying this trade-off, and the solubility of the acrylamide copolymer was rapidly improved by containing a very small amount of ionic groups, whereas a certain limited amount It was found that an anionic group of the above does not cause rapid aggregation in an actual papermaking system, and that the degree of aggregation is related to the viscosity values of the saline solution and the viscosity in pure water. That is, when the viscosity of the aqueous sodium chloride solution is compared with the viscosity of the pure aqueous solution of the acrylamide copolymer, if the viscosity of the aqueous sodium chloride solution is high, the paper material will not be intensively aggregated.
The viscosity of the saline solution, the viscosity higher acrylamide copolymer of pure water solution, specifically, 0.1 to 1 vinyl monomer units acrylamide copolymer has an anionic group. it can be 5 obtained as to have molar% free.
When the vinyl monomer having an anionic group is less than 0.1 mol%, the effect of improving the dissolution rate of the papermaking adhesive is small, and when it exceeds 1.5 mol%, the viscosity of the pure aqueous solution increases. In actual use examples, the paper material is aggregated. The vinyl monomer is more preferably 1.0 mol% or less.

アニオン性基を有するビニル系単量体としては、アクリル酸、アクリルアミド−２−メチルプロパンスルホン酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、およびこれらの塩等が例示され、これらの1種もしくは２種以上を使用することができる。中でもアクリル酸（塩）及び／又はアクリルアミド−２−メチルプロパンスルホン酸（塩）が工業的に安価で高品質のものが得られるので好ましく、アクリル酸（塩）が最も好ましいが、アニオン性基を含有する単量体であればこれに限られるものではない。
なお、本発明において、アクリル酸（塩）、アクリルアミド−２−メチルプロパンスルホン酸（塩）とは、アクリル酸及び／又はアクリル酸塩、アクリルアミド−２−メチルプロパンスルホン酸及び／又はアクリルアミド−２−メチルプロパンスルホン酸塩をそれぞれ示す。
また、アニオン性基は塩の形態をとっていることが好ましいが、部分的に中和されていなくてもかまわない。このようなアニオン性基を有するビニル系単量体は共重合によりアクリルアミド系共重合体に導入される。なお、アクリルアミド残基の加水分解による方法で、アクリルアミド系共重合体にアニオン性基を導入することも可能であるが、目標とされる導入量が少なく、許容幅も狭いため、加水分解を極力抑えた上、共重合によってアニオン性基を導入する事が好ましい。 Examples of the vinyl monomer having an anionic group include acrylic acid, acrylamide-2-methylpropanesulfonic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and salts thereof. 1 type, or 2 or more types can be used. Among them, acrylic acid (salt) and / or acrylamido-2-methylpropane sulfonic acid (salt) are preferable because they are industrially inexpensive and high quality can be obtained, and acrylic acid (salt) is most preferable. If it is a monomer to contain, it will not be restricted to this.
In the present invention, acrylic acid (salt) and acrylamide-2-methylpropane sulfonic acid (salt) are acrylic acid and / or acrylate, acrylamide-2-methylpropane sulfonic acid and / or acrylamide-2- Methyl propane sulfonate is shown respectively.
The anionic group is preferably in the form of a salt, but may not be partially neutralized. Such a vinyl monomer having an anionic group is introduced into an acrylamide copolymer by copolymerization. It is possible to introduce an anionic group into an acrylamide copolymer by a method based on hydrolysis of acrylamide residues. However, since the targeted introduction amount is small and the allowable range is narrow, hydrolysis is minimized. In addition, it is preferable to introduce an anionic group by copolymerization.

アクリルアミド系共重合体は、アクリルアミド及びアニオン性基を含むビニル系単量体のみが共重合したものであっても良いし、さらにその他のノニオン性単量体との共重合体であってもよい。上記のノニオン性単量体としては、メタアクリルアミド、Ｎ−ビニルアセトアミド、Ｎ−ビニルホルムアミド、Ｎ−ビニル−Ｎ−メチルアセトアミド、Ｎ−ビニル−Ｎ−メチルホルムアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、メチル（メタ）アクリレート、酢酸ビニル、アリルアルコール、Ｎ−ビニルピロリドン、イソプロピルアクリルアミド、ダイアセトンアクリルアミド、アクリロニトリル等が挙げられる。アクリルアミド以外のノニオン性単量体は２種以上用いられても良い。
アクリルアミドは全単量体に対して５０質量%以上が好ましく、７０質量%以上がより好ましく、特に９０質量％以上が好ましい。一般にアクリルアミドの割合が高いほど得られる重合体の分子量が大きくなる傾向があり、粘性の高いアクリルアミド系共重合体が得られる。 The acrylamide copolymer may be a copolymer of acrylamide and a vinyl monomer containing an anionic group, or may be a copolymer with another nonionic monomer. . Examples of the nonionic monomer include methacrylamide, N-vinylacetamide, N-vinylformamide, N-vinyl-N-methylacetamide, N-vinyl-N-methylformamide, N-methyl (meth) acrylamide, N , N-dimethyl (meth) acrylamide, methyl (meth) acrylate, vinyl acetate, allyl alcohol, N-vinylpyrrolidone, isopropylacrylamide, diacetone acrylamide, acrylonitrile and the like. Two or more nonionic monomers other than acrylamide may be used.
Acrylamide is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more based on the total monomers. In general, the higher the proportion of acrylamide, the higher the molecular weight of the polymer obtained, and a highly viscous acrylamide copolymer can be obtained.

また、アクリルアミド系共重合体は、抄紙用粘剤として使用されるものであるから、溶解性を悪化させない範囲で粘度が高いほど好ましく、具体的には、前記１質量％純水溶液の粘度が２０００ｍＰａ・ｓ以上であることが好ましい。   In addition, since the acrylamide copolymer is used as a papermaking adhesive, it is preferable that the viscosity is higher in a range not deteriorating the solubility. Specifically, the viscosity of the 1% by mass pure aqueous solution is 2000 mPa. -It is preferable that it is more than s.

本発明の抄紙用粘剤は、アクリルアミド系共重合体以外の成分をさらに含んでもよく、例えば通常抄紙用途に用いられるポリエチレンオキサイド、トロロアオイ抽出粘液等を含んでよい。但し、本発明の効果を発現させるためには、アクリルアミド系共重合体以外の成分はノニオン性の物質であることが好ましい。   The papermaking adhesive of the present invention may further contain components other than the acrylamide copolymer, and may contain, for example, polyethylene oxide, trolley extract mucus, etc. that are usually used for papermaking. However, in order to exhibit the effect of the present invention, it is preferable that the components other than the acrylamide copolymer are nonionic substances.

本発明の抄紙用粘剤は、さらにポリエチレンオキサイドを含有し、前記アクリルアミド系共重合体が２０〜７５質量％、ポリエチレンオキサイドが２５〜８０質量％であることが好ましい。
本発明に用いられる前記アクリルアミド系共重合体は、溶解速度が速いため、該アクリルアミド系共重合体とポリエチレンオキサイドとを混合して抄紙用粘剤として用いる際、アクリルアミド系共重合体とポリエチレンオキサイドとの溶解速度の差が小さく、溶解させるための時間を過度に延長する必要がないため、溶解時のポリエチレンオキサイドの劣化が最小限に抑えられる。しかも、前記アクリルアミド系共重合体およびポリエチレンオキサイドを含むと、アクリルアミド系共重合体単独あるいはポリエチレンオキサイド単独と比較して、紙料を分散させる性能が向上するという相乗効果を得ることができる。また、ポリエチレンオキサイドの発泡の問題も発生しない。
ポリエチレンオキサイドの含有比率が８０質量％以下であると抄紙用粘剤のコストが低くなり、ポリエチレンオキサイドの含有比率が２５質量%以上であると、抄紙用粘剤としての性能を表す、抄紙用粘剤のピペット粘度の値が、ポリエチレンオキサイド単独の値より大きくなり、即ち、より少量の抄紙用粘剤で安定した抄紙を行うことができる。
ポリエチレンオキサイドの含有比率の下限は３３質量％がさらに好ましく、４０質量％が特に好ましい。ポリエチレンオキサイドの含有比率の上限は７５質量％がさらに好ましく、６７質量％が特に好ましい。
なお、ポリエチレンオキサイドとアクリルアミド系共重合体との含有比率が１対１に近づくほど、ポリエチレンオキサイド単独水溶液のピペット粘度、アクリルアミド系共重合体単独水溶液のピペット粘度、あるいはポリエチレンオキサイドとアクリルアミド系共重合体の抄紙用粘剤における含有比率に応じた相加平均値よりも、抄紙用粘剤のピペット粘度が向上する相乗効果が大きくなる。 The papermaking adhesive of the present invention further contains polyethylene oxide, preferably 20 to 75% by mass of the acrylamide copolymer and 25 to 80% by mass of polyethylene oxide.
Since the acrylamide copolymer used in the present invention has a high dissolution rate, when the acrylamide copolymer and polyethylene oxide are mixed and used as a papermaking adhesive, the acrylamide copolymer and polyethylene oxide The difference in dissolution rate is small, and it is not necessary to excessively extend the time for dissolution, so that deterioration of polyethylene oxide during dissolution is minimized. In addition, when the acrylamide copolymer and polyethylene oxide are included, a synergistic effect that the performance of dispersing the paper material is improved as compared with the acrylamide copolymer alone or polyethylene oxide alone can be obtained. Moreover, the problem of foaming of polyethylene oxide does not occur.
When the content ratio of polyethylene oxide is 80% by mass or less, the cost of the papermaking adhesive becomes low, and when the content ratio of polyethylene oxide is 25% by mass or more, it represents the performance as a papermaking adhesive. The pipette viscosity value of the agent is larger than that of polyethylene oxide alone, that is, stable papermaking can be performed with a smaller amount of papermaking viscosity.
The lower limit of the content ratio of polyethylene oxide is more preferably 33% by mass, and particularly preferably 40% by mass. The upper limit of the content ratio of polyethylene oxide is more preferably 75% by mass, and particularly preferably 67% by mass.
As the content ratio of polyethylene oxide and acrylamide copolymer approaches 1: 1, the pipette viscosity of the polyethylene oxide single aqueous solution, the pipette viscosity of the acrylamide copolymer single aqueous solution, or the polyethylene oxide and acrylamide copolymer The synergistic effect of improving the pipette viscosity of the papermaking adhesive is greater than the arithmetic mean value corresponding to the content ratio in the papermaking adhesive.

本発明に用いられるアクリルアミド系共重合体の製造方法は、食塩水溶液の粘度が純水溶液の粘度より高いアクリルアミド系共重合体を得ることができれば特に限定されず、水溶液重合、懸濁重合などの公知の重合方法を採用することができる。アクリルアミド系共重合体の一般的な重合方法は、ラジカル重合開始剤や光重合開始剤を用いた水溶液重合であるが、光重合開始剤を用いた水溶液重合が特に好ましい。
水溶液重合において、水溶液中のアクリルアミドの濃度（以下、「単量体濃度」と略す。）は通常１０〜７５質量％であるが、単量体濃度の下限は１５質量％以上が好ましく、２０質量％以上がより好ましい。一方、単量体濃度の上限は５０質量％以下が好ましい。
単量体濃度が高くなると生産性が向上する傾向があり、単量体濃度が低くなると、得られる重合体の溶解性が向上する傾向がある。 The method for producing the acrylamide copolymer used in the present invention is not particularly limited as long as an acrylamide copolymer in which the viscosity of the saline solution is higher than that of the pure aqueous solution can be obtained, and known methods such as aqueous solution polymerization and suspension polymerization are known. The polymerization method can be employed. A general polymerization method of the acrylamide copolymer is aqueous solution polymerization using a radical polymerization initiator or a photopolymerization initiator, but aqueous solution polymerization using a photopolymerization initiator is particularly preferable.
In aqueous solution polymerization, the concentration of acrylamide in the aqueous solution (hereinafter abbreviated as “monomer concentration”) is usually 10 to 75% by mass, but the lower limit of the monomer concentration is preferably 15% by mass or more, and 20% by mass. % Or more is more preferable. On the other hand, the upper limit of the monomer concentration is preferably 50% by mass or less.
When the monomer concentration is high, productivity tends to be improved, and when the monomer concentration is low, solubility of the resulting polymer tends to be improved.

通常重合開始剤としては、光重合開始剤、アゾ系開始剤、レドックス系開始剤等が使用できる。
光重合開始剤としては、α−ヒドロキシケトン類、アシルホスフィンオキサイド化合物等が使用できる。これらの化合物の例としては、アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、２，２−アゾビス（２−アミジノプロパン）ジハイドロクロライド、２，２−アゾビス［２−メチル−Ｎ−（２−ハイドロキシエチル）−プロピオンアミド］、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２，４，６−トリメチチルベンゾイルジフェニルホスフィンオキサイド、ベンゾイン、ベンゾインエチルエーテル、ベンゾフェノン等が挙げられる。
アゾ系開始剤は光重合開始剤や熱分解重合開始剤として利用でき、例えば、アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、２，２’−アゾビス（２−アミジノプロパン）ジハイドロクロライド、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］ジハイドロクロライド、２，２’−アゾビス［２−メチル−N−（２−ヒドロキシエチル）−プロピオンアミド等が挙げられる。
レドックス系開始剤としては、過硫酸塩やｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、過酸化ベンゾイル、過酸化ラウロイル等の過酸化物と、亜硫酸塩、亜硫酸水素塩、チオ硫酸塩、ナトリウムホルムアルデヒドスルホキシレート、硫酸第一鉄、ブドウ糖、アミン類等の還元剤との組み合わせが挙げられる。
重合開始剤は単独あるいは２種以上の併用のいずれでも良い。重合開始剤の添加量は、得られる重合体の分子量や重合時間または残存モノマー量の兼ね合いで決定され、例えば、光重合開始剤の場合、全単量体に対して通常１〜１０００ｐｐｍ程度である。 Usually, as the polymerization initiator, a photopolymerization initiator, an azo initiator, a redox initiator, or the like can be used.
As the photopolymerization initiator, α-hydroxy ketones, acylphosphine oxide compounds and the like can be used. Examples of these compounds include azobisisobutyronitrile, azobisisovaleronitrile, 2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis [2-methyl-N- (2 -Hydroxyethyl) -propionamide], 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylylbenzoyldiphenylphosphine oxide, benzoin, benzoin ethyl ether And benzophenone.
The azo initiator can be used as a photopolymerization initiator or a thermal decomposition polymerization initiator. For example, azobisisobutyronitrile, azobisisovaleronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide and the like. .
Redox initiators include persulfates, peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, sulfites, bisulfites, thiosulfates, sodium formaldehyde The combination with reducing agents, such as a sulfoxylate, ferrous sulfate, glucose, and amines, is mentioned.
The polymerization initiator may be used alone or in combination of two or more. The addition amount of the polymerization initiator is determined in consideration of the molecular weight of the polymer to be obtained, the polymerization time, or the residual monomer amount. For example, in the case of a photopolymerization initiator, it is usually about 1 to 1000 ppm with respect to all monomers. .

通常、抄紙用粘剤は粉末で使用されるので、得られたアクリルアミド系共重合体は乾燥され粉末化される。乾燥方法は特に規定されないが、加水分解やアクリルアミド系共重合体の溶解性の悪化を防ぐため、熱負荷の小さい乾燥方法を取ることが望ましい。
アクリルアミド系共重合体は、乾燥に続いて粉砕され粉末化される。粒径は特に規定はないが、大きすぎれば溶解に時間がかかり、小さければ粉立ちなどの問題が生じることがある。 Usually, since the papermaking adhesive is used as a powder, the obtained acrylamide copolymer is dried and powdered. Although a drying method is not particularly defined, it is desirable to take a drying method with a small heat load in order to prevent hydrolysis and deterioration of the solubility of the acrylamide copolymer.
The acrylamide copolymer is pulverized and powdered after drying. The particle size is not particularly defined, but if it is too large, it takes time to dissolve, and if it is small, problems such as powdering may occur.

得られたアクリルアミド系共重合体は溶解性が良いことが好ましい。ここで、溶解性は、水３ｋｇにアクリルアミド系共重合体を０．１質量％添加し、３時間撹拌後、目開き１８０μｍの金網でろ過し、金網上に補足された含水ゲルの質量で評価される。その量は少ないほど良く、通常含水ゲル質量が２０ｇ以下、好ましくは１０ｇ以下さらに好ましくは６ｇ以下である。   The obtained acrylamide copolymer preferably has good solubility. Here, the solubility is evaluated by the mass of a hydrogel supplemented on a wire mesh by adding 0.1% by mass of an acrylamide copolymer to 3 kg of water, stirring for 3 hours, filtering through a wire mesh having an opening of 180 μm. Is done. The smaller the amount, the better. Usually, the hydrogel mass is 20 g or less, preferably 10 g or less, more preferably 6 g or less.

得られたアクリルアミド系共重合体の粉末を単独で、あるいはポリエチレンオキサイドをさらに混合して、抄紙用粘剤として用いることができる。
本発明の抄紙用粘剤において、上記のようにポリエチレンオキサイドをさらに含有させる場合、ポリエチレンオキサイドとアクリルアミド系共重合体の混合は粉体同士で予め混合するか、溶解時に粉体を別々に供給し、溶解槽中で混合することもできる。また、ポリエチレンオキサイドとアクリルアミド系共重合体を別々に溶解し、水溶液どうしを混合しても良い。水溶液の状態で混合する場合は、さらに均一にするため撹拌混合が必要である。
なお、本発明の抄紙用粘剤を、前記アクリルアミド系共重合体のみから構成して流通させ、抄紙の際に他の市販の抄紙用粘剤、例えばポリエチレンオキサイド系抄紙用粘剤と粉体同士で混合したり、溶解槽中で混合して抄紙に用いることもできる。このように、本発明の抄紙用粘剤を他の抄紙用粘剤と混合しても、他の抄紙用粘剤の劣化を招くことはなく、良好に性能を発揮することができる。 The obtained acrylamide copolymer powder can be used alone or in combination with polyethylene oxide as a papermaking adhesive.
In the papermaking adhesive of the present invention, when the polyethylene oxide is further contained as described above, the polyethylene oxide and the acrylamide copolymer are mixed in advance with each other, or the powder is supplied separately at the time of dissolution. It is also possible to mix in a dissolution tank. Further, polyethylene oxide and acrylamide copolymer may be dissolved separately, and aqueous solutions may be mixed. In the case of mixing in the state of an aqueous solution, stirring and mixing are necessary to make it more uniform.
In addition, the papermaking adhesive of the present invention is composed and distributed only from the acrylamide-based copolymer, and during the papermaking, other commercially available papermaking adhesives, for example, polyethylene oxide papermaking adhesives and powders. Or mixed in a dissolution tank and used for papermaking. Thus, even if the papermaking adhesive of the present invention is mixed with other papermaking adhesives, other papermaking adhesives will not be deteriorated and performance can be exhibited well.

上述のように、本発明の抄紙用粘剤は、含有しているアクリルアミド系共重合体の前記食塩水溶液の粘度が純水溶液の粘度より高いので、アクリルアミド系共重合体中のアニオン性基を有する単量体単位が少ない。
その結果、カチオン性薬剤と併用した際の紙料繊維の凝集が防止され、抄紙における分散が良好となり、抄紙の安定性、製造効率を向上させることができる。さらに、少量存在しているアニオン性基を有する単量体単位の働きで溶解速度が早く、使いやすいと共に、不溶解物が少ない利点がある。また、安価で抄紙性能に優れている。
しかも、ポリエチレンオキサイドをさらに含有した場合も従来のようなポリエチレンオキサイドの劣化の問題を起こさず、ポリエチレンオキサイドをさらに含めば、さらに増粘効果、ひいては紙料繊維を分散させる性能が向上するので、抄紙の安定性、製造効率が向上される上に、抄紙用粘剤の使用量が低減される。 As described above, since the viscosity of the saline solution of the acrylamide copolymer contained in the papermaking adhesive of the present invention is higher than that of a pure aqueous solution, it has an anionic group in the acrylamide copolymer. There are few monomer units.
As a result, the aggregation of the paper fibers when used in combination with the cationic agent is prevented, the dispersion in the papermaking becomes good, and the papermaking stability and production efficiency can be improved. Furthermore, the action of the monomer unit having an anionic group present in a small amount has an advantage that the dissolution rate is fast and easy to use, and there are few insolubles. In addition, it is inexpensive and has excellent papermaking performance.
Moreover, even when polyethylene oxide is further contained, it does not cause the problem of deterioration of polyethylene oxide as in the past, and if polyethylene oxide is further included, the thickening effect and thus the performance to disperse the paper fiber are improved. In addition to improving the stability and production efficiency, the amount of the papermaking adhesive used is reduced.

以下、実施例および比較例により本発明をさらに詳しく説明するが、本発明はこれらに何ら限定されるものではない。
〈実施例１〉
〔アクリルアミド系共重合体の調製〕
アクリルアミドとアクリル酸ナトリウムの共重合体からなる、アクリル酸塩０．４モル％含有アクリルアミド系共重合体を調製した。
１リットル三角フラスコに５０質量％アクリルアミド水溶液３２９．０５ｇ、５０質量％アクリル酸水溶液１．３５ｇ、３３質量％水酸化ナトリウム水溶液１．１４ｇ、亜リン酸二ナトリウム５０ｐｐｍ（以下、ｐｐｍ表示は全液量に対する質量割合を示す）を含有した水溶液４１３ｇを入れて単量体水溶液を調整した。
遮光下で２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン１０ｐｐｍおよび２，２’−アゾビス（２−アミジノプロパン）ジハイドロクロライド１５０ｐｐｍを単量体水溶液に加え、三角フラスコを１０℃の恒温水槽に入れ、そのまま３０分間窒素ガスで水溶液中の溶存酸素を置換した。
厚さ１ｍｍのステンレス板の周縁に、該ステンレス板の内底面が２００×２００ｍｍの正方形になるように断面の一辺が２４ｍｍのゴム棒を貼り付けてある容器を用意した。この容器の内側に厚さ１６μｍの光透過性フィルム（厚さ１２μｍのポリエチレンテレフタレートおよび厚さ４μｍのポリ塩化ビニリデンからなる積層フィルム）を敷き、このフィルム上に重合性単量体の水溶液を供給した。水溶液の上面を、水溶液と接するように上記と同種の光透過性フィルムで覆った。単量体水溶液からなる層の厚さは１０ｍｍであった。また、ステンレス板の裏側を、単量体水溶液を供給する前から１０℃の水を吹き付け冷却し、ステンレス板の温度を１０℃に調節した。さらに、重合終了まで１０℃の水を吹き付けることを継続した。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these at all.
<Example 1>
[Preparation of acrylamide copolymer]
An acrylamide copolymer containing 0.4 mol% of acrylate, consisting of a copolymer of acrylamide and sodium acrylate, was prepared.
In a 1 liter Erlenmeyer flask, 329.05 g of 50% by mass acrylamide aqueous solution, 1.35 g of 50% by mass acrylic acid aqueous solution, 1.14 g of 33% by mass sodium hydroxide aqueous solution, 50 ppm disodium phosphite (hereinafter, ppm display is the total liquid amount) An aqueous monomer solution was prepared by adding 413 g of an aqueous solution containing a mass ratio of
Under shading, 2-hydroxy-2-methyl-1-phenylpropan-1-one 10 ppm and 2,2′-azobis (2-amidinopropane) dihydrochloride 150 ppm were added to the monomer aqueous solution, and the Erlenmeyer flask was placed at 10 ° C. And dissolved oxygen in the aqueous solution was replaced with nitrogen gas for 30 minutes.
A container was prepared in which a rubber rod having a side of a cross section of 24 mm was attached to the periphery of a stainless steel plate having a thickness of 1 mm so that the inner bottom surface of the stainless steel plate was a 200 × 200 mm square. A light-transmitting film having a thickness of 16 μm (a laminated film made of polyethylene terephthalate having a thickness of 12 μm and polyvinylidene chloride having a thickness of 4 μm) was laid on the inside of the container, and an aqueous solution of a polymerizable monomer was supplied onto the film. . The upper surface of the aqueous solution was covered with a light transmissive film of the same kind as described above so as to be in contact with the aqueous solution. The thickness of the layer composed of the monomer aqueous solution was 10 mm. Further, the back side of the stainless steel plate was cooled by spraying water at 10 ° C. before supplying the monomer aqueous solution, and the temperature of the stainless steel plate was adjusted to 10 ° C. Furthermore, spraying water at 10 ° C. was continued until the polymerization was completed.

単量体水溶液の供給された容器の上方に、２０Ｗ型蛍光ケミカルランプを設置した。あらかじめ水溶液表面で照射強度が５Ｗ／ｍ2 となるように調整した蛍光ケミカルランプを１０分間点灯した。次に、水溶液表面で照射強度が１０Ｗ／ｍ2 となるように調整した蛍光ケミカルランプを２０分間点灯した。さらに、水溶液表面で照射強度が６０Ｗ／ｍ2 となるように調整した蛍光ケミカルランプを３０分間点灯し、重合を完結させ、重合体を含む含水ゲル状シートを得た。水溶液もしくは含水ゲル状シートが達した重合時のピーク温度は５５℃であった。
得られた含水ゲル状シートをはさみで細断し、６０℃の熱風乾燥機で乾燥した。さらに、乾燥物をウイレー式粉砕機で粉砕し、粉末状のアクリルアミド系共重合体を得た。 A 20 W fluorescent chemical lamp was installed above the container to which the aqueous monomer solution was supplied. Irradiation intensity in a pre-solution surface is a fluorescent chemical lamp was adjusted so that 5W / m 2 lit. 10 minutes. Next, a fluorescent chemical lamp adjusted to have an irradiation intensity of 10 W / m 2 on the surface of the aqueous solution was lit for 20 minutes. Furthermore, a fluorescent chemical lamp adjusted to have an irradiation intensity of 60 W / m 2 on the surface of the aqueous solution was lit for 30 minutes to complete the polymerization, and a hydrous gel-like sheet containing a polymer was obtained. The peak temperature during polymerization that the aqueous solution or hydrogel sheet reached was 55 ° C.
The obtained hydrogel sheet was shredded with scissors and dried with a hot air dryer at 60 ° C. Further, the dried product was pulverized with a Wiley pulverizer to obtain a powdery acrylamide copolymer.

〔アクリルアミド系共重合体の水溶液物性の評価〕
（１）純水溶液の粘度の測定
得られたアクリルアミド系共重合体の１質量％純水溶液の粘度を測定した。
５００ｍｌビーカーに純水４９５ｇを入れ、撹拌下に、上記で得られたアクリルアミド系共重合体５ｇを添加し撹拌を３時間継続した後、２５℃においてＢ型粘度計にて粘度測定した。その際に使用したローターはＮｏ．２で回転数６ｒｐｍとした。
（２）食塩水溶液の粘度の測定
得られたアクリルアミド系共重合体の１質量％食塩水溶液の粘度を測定した。
５００ｍｌビーカーに純水４７５ｇをいれ、撹拌下にアクリルアミド系共重合体５ｇを添加し、３時間撹拌した。さらに、食塩２０ｇを添加し、３０分撹拌した後、２５℃においてＢ型粘度計により粘度測定した。その際に使用したローターは上記と同様とした。
（３）水不溶解分の測定
３０００ｍｌビーカーに水道水２９９７ｇを入れ、撹拌下にアクリルアミド系共重合体３ｇを添加し、３時間溶解した後、目開き１８０μｍの金網で濾過し、１０分間放置後質量を測定した。そして、予め測定しておいた金網の質量を差し引いて水不溶解分の質量とした。
（４）溶解時間の測定
３０００ｍｌビーカーに水道水２９９７ｇを入れ、撹拌下にアクリルアミド系共重合体３ｇを添加し、所定時間溶解した後、目開き１８０μｍの金網で濾過し、１０分間放置後、金網上に残留した含水ゲル状物の質量を測定した。予め測定しておいた金網の質量を差し引いた質量を測定した。前記測定を溶解時間が３０分、６０分、９０分、１２０分、１５０分、１８０分で行い、質量が実質的に変わらなくなった時間を溶解時間とした。 [Evaluation of aqueous solution properties of acrylamide copolymer]
(1) Measurement of viscosity of pure aqueous solution The viscosity of a 1% by mass pure aqueous solution of the obtained acrylamide copolymer was measured.
495 g of pure water was put into a 500 ml beaker, 5 g of the acrylamide copolymer obtained above was added with stirring, and stirring was continued for 3 hours, and then the viscosity was measured with a B-type viscometer at 25 ° C. The rotor used at that time was No. 2 and the rotation speed was 6 rpm.
(2) Measurement of viscosity of saline solution The viscosity of a 1% by mass saline solution of the obtained acrylamide copolymer was measured.
In a 500 ml beaker, 475 g of pure water was added, and 5 g of an acrylamide copolymer was added with stirring, followed by stirring for 3 hours. Further, 20 g of sodium chloride was added and stirred for 30 minutes, and then the viscosity was measured with a B-type viscometer at 25 ° C. The rotor used at that time was the same as described above.
(3) Measurement of water-insoluble matter Add 2997 g of tap water to a 3000 ml beaker, add 3 g of acrylamide copolymer with stirring, dissolve for 3 hours, filter through a wire mesh with an opening of 180 μm, and leave for 10 minutes. The mass was measured. And the mass of the wire mesh measured beforehand was subtracted and it was set as the mass of water insoluble matter.
(4) Measurement of dissolution time 2997 g of tap water was put into a 3000 ml beaker, 3 g of acrylamide copolymer was added with stirring, dissolved for a predetermined time, filtered through a wire mesh having an opening of 180 μm, and allowed to stand for 10 minutes. The mass of the hydrated gel remaining on the top was measured. The mass obtained by subtracting the mass of the wire mesh measured in advance was measured. The measurement was performed at dissolution times of 30 minutes, 60 minutes, 90 minutes, 120 minutes, 150 minutes, and 180 minutes, and the time when the mass did not substantially change was defined as the dissolution time.

〔紙料スラリーの調整〕
紙料として、叩解度６５０ｍｌＣＦＳ（カナダ標準濾水度）のＮＢＫＰ（針葉樹パルプ）を用い、０．２質量％のパルプスラリーを調整した。この際、添加薬剤としてカチオン性の湿潤紙力増強剤であるポリアミドポリアミンエピクロルヒドリンをパルプに対して０．２質量％添加し、充分撹拌してパルプスラリーを得た。 [Adjustment of paper slurry]
NBKP (conifer pulp) having a beating degree of 650 ml CFS (Canadian standard freeness) was used as a paper material, and a 0.2% by mass pulp slurry was prepared. At this time, 0.2% by mass of polyamide polyamine epichlorohydrin, which is a cationic wet paper strength enhancer, was added as an additive to the pulp and sufficiently stirred to obtain a pulp slurry.

〔抄紙用粘剤の性能評価〕
上記で得られたアクリルアミド系共重合体の粉末からなる抄紙用粘剤について、性能を評価した。
上記紙料スラリーに対し、０．１質量％の濃度で溶解した抄紙用粘剤水溶液を抄紙用粘剤の純分として２ｐｐｍとなるように添加し、撹拌混合したスラリー溶液について紙料凝集性、濾水性を測定した。
（１）紙料凝集性
抄紙用粘剤が添加されている紙料スラリー溶液をジャーテスターで撹拌した際の、紙料の様子を目視判定した。評価基準を以下に示す。
◎：凝集性がなく使用に際して全く問題ない。
○：僅かに凝集するが、使用に際し問題がない。
△：少し凝集し、抄紙された製品の地合が乱れる可能性がある。
×：凝集し抄紙に使用できない。
（２）濾水性
濾布を敷いた孔径６２ｍｍのヌッチェを５００ｍｌメスシリンダーの上に設置し、抄紙用粘剤を添加混合した紙料スラリーをヌッチェにあけ、濾水量を測定した。
ここで、濾水量が少ないほど紙料の分散性が良好であることを示し、紙料に一定の分散性を付与するために必要な粘剤使用量が少なくて済むことを意味する。
（３）紙の地合
フィルター等を通さずに抄紙用粘剤を直接添加した紙料スラリー溶液を用いて、円網ヤンキー式抄紙機により抄紙した坪量１３．０ｇ／ｍ２の紙を目視判定した。評価基準を以下に示す。
◎：均一で優れる。
○：良好。
△：不均一。
×：不良で抄紙不可能または穴が空いた紙である。
（４）発泡性
抄紙用粘剤を０．１質量％の濃度で溶解させた水溶液に空気を吹き込んで発泡の有無を目視で評価した。評価基準を以下に示す。
○：発泡なし。
△：多少発泡し、抄紙のためには消泡剤の添加が必要である。
×：発泡が多く、抄紙のためには多量の消泡剤を必要とする。
抄紙用粘剤の評価結果を表２にまとめて示した。 [Performance evaluation of paper making adhesive]
The performance of the adhesive for papermaking made of the acrylamide copolymer powder obtained above was evaluated.
To the above paper slurry, an aqueous papermaking adhesive solution dissolved at a concentration of 0.1% by mass is added to 2 ppm as a pure content of the papermaking adhesive. The freeness was measured.
(1) Paper cohesiveness The state of the paper stock when the paper slurry solution to which the papermaking adhesive was added was stirred with a jar tester was visually determined. The evaluation criteria are shown below.
(Double-circle): There is no cohesion and there is no problem at the time of use.
○: Slightly agglomerates, but no problem in use.
(Triangle | delta): It may aggregate a little and the formation of the paper-made product may be disordered.
X: Aggregates and cannot be used for papermaking.
(2) Drainage A Nutsche with a hole diameter of 62 mm with filter cloth was placed on a 500 ml graduated cylinder, and a stock slurry mixed with a papermaking adhesive was added to Nutsche, and the amount of drainage was measured.
Here, the smaller the amount of drainage, the better the dispersibility of the paper material, which means that the amount of the sticky agent used for imparting a certain dispersibility to the paper material can be reduced.
(3) Formation of paper Using a paper slurry solution in which a papermaking adhesive is directly added without passing through a filter or the like, a paper having a basis weight of 13.0 g / m 2 is visually observed using a circular mesh Yankee type paper machine. Judged. The evaluation criteria are shown below.
A: Uniform and excellent.
○: Good.
Δ: Non-uniform.
X: Paper that is defective and cannot be made or has holes.
(4) Foamability Air was blown into an aqueous solution in which a papermaking adhesive was dissolved at a concentration of 0.1% by mass, and the presence or absence of foaming was visually evaluated. The evaluation criteria are shown below.
○: No foaming.
Δ: Foamed somewhat, and it is necessary to add an antifoaming agent for papermaking.
X: Much foaming and a large amount of antifoaming agent is required for papermaking.
Table 2 summarizes the evaluation results of the papermaking adhesive.

〈実施例２〉
５０質量％アクリルアミド水溶液３２８．３８ｇ、５０質量％アクリル酸水溶液２．０２ｇ、３３質量％水酸化ナトリウム水溶液１．７０ｇとして単量体水溶液を調整した以外は実施例１と同様の方法で重合を行い、アクリル酸塩０．６モル％含有アクリルアミド系共重合体を得た。アクリルアミド系共重合体の水溶液物性の評価結果を表１に、得られたアクリルアミド系共重合体からなる抄紙用粘剤の評価結果を表２にそれぞれ示した。
〈実施例３〉
５０質量％アクリルアミド水溶液３２７．７２ｇ、５０質量％アクリル酸水溶液２．６８ｇ、３３質量％水酸化ナトリウム水溶液２．２５ｇとして単量体水溶液を調整した以外は実施例１と同様の方法で重合を行い、アクリル酸塩０．８モル％含有アクリルアミド系共重合体を得た。アクリルアミド系共重合体の水溶液物性の評価結果を表１に、得られたアクリルアミド系共重合体からなる抄紙用粘剤の評価結果を表２にそれぞれ示した。
〈実施例４〉
５０質量％アクリルアミド水溶液３２７．０６ｇ、５０質量％アクリル酸水溶液３．３４ｇ、３３質量％水酸化ナトリウム水溶液２．８１ｇとした以外は実施例１と同様の方法で重合を行い、アクリル酸塩１．０モル％含有アクリルアミド系共重合体を得た。アクリルアミド系共重合体の水溶液物性の評価結果を表１に、得られたアクリルアミド系共重合体からなる抄紙用粘剤の評価結果を表２にそれぞれ示した。
〈実施例５〉
５０質量％アクリルアミド水溶液３２５．３８ｇ、５０質量％アクリル酸水溶液５．０２ｇ、３３質量％水酸化ナトリウム水溶液４．２３ｇとした以外は実施例１と同様の方法で重合を行い、アクリル酸塩１．５モル％含有アクリルアミド系共重合体を得た。アクリルアミド系共重合体の水溶液物性の評価結果を表１に、得られたアクリルアミド系共重合体からなる抄紙用粘剤の評価結果を表２にそれぞれ示した。 <Example 2>
Polymerization was carried out in the same manner as in Example 1 except that the monomer aqueous solution was adjusted as 328.38 g of 50% by mass acrylamide aqueous solution, 2.02 g of 50% by mass acrylic acid aqueous solution and 1.70 g of 33% by mass sodium hydroxide aqueous solution. An acrylamide copolymer containing 0.6 mol% of acrylate was obtained. Table 1 shows the evaluation results of the aqueous solution properties of the acrylamide copolymer, and Table 2 shows the evaluation results of the papermaking adhesive made of the obtained acrylamide copolymer.
<Example 3>
Polymerization was carried out in the same manner as in Example 1 except that the monomer aqueous solution was adjusted as 32.72 g of 50% by mass acrylamide aqueous solution, 2.68 g of 50% by mass acrylic acid aqueous solution and 2.25 g of 33% by mass sodium hydroxide aqueous solution. An acrylamide copolymer containing 0.8 mol% of acrylate was obtained. Table 1 shows the evaluation results of the aqueous solution properties of the acrylamide copolymer, and Table 2 shows the evaluation results of the papermaking adhesive made of the obtained acrylamide copolymer.
<Example 4>
Polymerization was carried out in the same manner as in Example 1 except that 327.06 g of 50% by mass acrylamide aqueous solution, 3.34 g of 50% by mass acrylic acid aqueous solution, and 2.81 g of 33% by mass sodium hydroxide aqueous solution were used. An acrylamide copolymer containing 0 mol% was obtained. Table 1 shows the evaluation results of the aqueous solution properties of the acrylamide copolymer, and Table 2 shows the evaluation results of the papermaking adhesive made of the obtained acrylamide copolymer.
<Example 5>
Polymerization was carried out in the same manner as in Example 1 except that 325.38 g of 50% by mass acrylamide aqueous solution, 5.02 g of 50% by mass acrylic acid aqueous solution, and 4.23 g of 33% by mass sodium hydroxide aqueous solution were used. An acrylamide copolymer containing 5 mol% was obtained. Table 1 shows the evaluation results of the aqueous solution properties of the acrylamide copolymer, and Table 2 shows the evaluation results of the papermaking adhesive made of the obtained acrylamide copolymer.

〈比較例１〉
５０質量％アクリルアミド水溶液３３０．４０ｇ、５０質量％アクリル酸水溶液０ｇ、３３質量％水酸化ナトリウム水溶液０ｇとした以外は実施例１と同様の方法で重合を行い、アクリル酸塩０モル％含有アクリルアミド系共重合体を得た。アクリルアミド系共重合体の水溶液物性の評価結果を表１に、得られたアクリルアミド系共重合体からなる抄紙用粘剤の評価結果を表２にそれぞれ示した。
〈比較例２〉
５０質量％アクリルアミド水溶液３２３．６９ｇ、５０質量％アクリル酸水溶液６．７１ｇ、３３質量％水酸化ナトリウム水溶液５．６５ｇとした以外は実施例１と同様の方法で重合を行い、アクリル酸塩２．０モル％含有アクリルアミド系共重合体を得た。アクリルアミド系共重合体の水溶液物性の評価結果を表１に、抄紙用粘剤の評価結果を表２にそれぞれ示した。
〈比較例３〉
５０質量％アクリルアミド水溶液３１３．６５ｇ、５０質量％アクリル酸水溶液１６．７５ｇ、３３質量％水酸化ナトリウム水溶液１４．１０ｇとした以外は実施例１と同様の方法で重合を行い、アクリル酸塩５．０モル％含有アクリルアミド系共重合体を得た。アクリルアミド系共重合体の水溶液物性の評価結果を表１に、得られたアクリルアミド系共重合体からなる抄紙用粘剤の評価結果を表２にそれぞれ示した。 <Comparative example 1>
Polymerization was carried out in the same manner as in Example 1 except that 330.40 g of 50% by mass acrylamide aqueous solution, 0 g of 50% by mass acrylic acid aqueous solution and 0 g of 33% by mass sodium hydroxide aqueous solution were used. A copolymer was obtained. Table 1 shows the evaluation results of the aqueous solution properties of the acrylamide copolymer, and Table 2 shows the evaluation results of the papermaking adhesive made of the obtained acrylamide copolymer.
<Comparative example 2>
Polymerization was carried out in the same manner as in Example 1 except that 323.69 g of 50% by mass acrylamide aqueous solution, 6.71 g of 50% by mass acrylic acid aqueous solution, and 5.65 g of 33% by mass sodium hydroxide aqueous solution were used. An acrylamide copolymer containing 0 mol% was obtained. The evaluation results of the aqueous solution physical properties of the acrylamide copolymer are shown in Table 1, and the evaluation results of the papermaking adhesive are shown in Table 2, respectively.
<Comparative Example 3>
Polymerization was carried out in the same manner as in Example 1 except that 313.65 g of a 50% by mass acrylamide aqueous solution, 16.75 g of a 50% by mass acrylic acid aqueous solution, and 14.10 g of a 33% by mass sodium hydroxide aqueous solution were used. An acrylamide copolymer containing 0 mol% was obtained. Table 1 shows the evaluation results of the aqueous solution properties of the acrylamide copolymer, and Table 2 shows the evaluation results of the papermaking adhesive made of the obtained acrylamide copolymer.

Figure 0004522692
Figure 0004522692

Figure 0004522692
Figure 0004522692

以上表１、表２に示されるように、アクリルアミドにアニオン性基を有するビニル系単量体が共重合したアクリルアミド系共重合体を含み、該アクリルアミド系共重合体と食塩４質量％とを含む食塩水溶液の粘度が、前記食塩水溶液と同じ濃度のアクリルアミド系共重合体を純水中に含む純水溶液の粘度より高かった実施例１〜５では、紙料凝集性、濾水性が低く、紙の地合に優れて、しかも溶解時間が短い取り扱い性にも優れた抄紙用粘剤が得られた。
一方、アニオン性基が全くない比較例１は抄紙性能的には優れたものであったが、溶解速度が遅く、溶解に時間がかかる取り扱い難いものであった。また、アニオン性基を多く含みアクリルアミド系共重合体の純水溶液の粘度が食塩水溶液の粘度より高かった比較例２、３では、紙料凝集性、濾水性が高く、紙の地合が不良であった。 As shown in Tables 1 and 2 above, it includes an acrylamide copolymer in which a vinyl monomer having an anionic group is copolymerized with acrylamide, and includes the acrylamide copolymer and 4% by mass of sodium chloride. In Examples 1 to 5 in which the viscosity of the saline solution was higher than the viscosity of the pure aqueous solution containing the acrylamide copolymer in the pure water having the same concentration as that of the saline solution, the paper cohesiveness and the drainage were low. A papermaking adhesive having excellent texture and short dissolution time was obtained.
On the other hand, Comparative Example 1 having no anionic group was excellent in papermaking performance, but it was difficult to handle because the dissolution rate was slow and it took time to dissolve. Further, in Comparative Examples 2 and 3, in which the viscosity of the pure aqueous solution of the acrylamide copolymer containing a large amount of anionic groups was higher than the viscosity of the saline solution, the paper stock agglomeration and drainage were high, and the paper texture was poor. there were.

〈実施例６〜１０および比較例４〉
ポリエチレンオキサイドと、実施例２で使用したアクリルアミド系共重合体を表３に示す配合比率で混合して抄紙用粘剤とし、これらの抄紙用粘剤について実施例１と同様に評価を行った。ポリエチレンオキサイドは市販のアルコックスｓｗ（商品名、明成化学社製）を使用した。
結果をまとめて表３に示した。なお、表３において、ＰＥＯ、ＰＡＭは、ポリエチレンオキサイド、実施例２で使用したアクリルアミド系共重合体をそれぞれ示す。 <Examples 6 to 10 and Comparative Example 4>
Polyethylene oxide and the acrylamide copolymer used in Example 2 were mixed at the blending ratios shown in Table 3 to obtain papermaking adhesives, and these papermaking adhesives were evaluated in the same manner as in Example 1. As the polyethylene oxide, commercially available Alcox sw (trade name, manufactured by Meisei Chemical Co., Ltd.) was used.
The results are summarized in Table 3. In Table 3, PEO and PAM represent polyethylene oxide and the acrylamide copolymer used in Example 2, respectively.

Figure 0004522692
Figure 0004522692

表３に示されるように、ポリエチレンオキサイドと、実施例２のアクリルアミド系共重合体とを含有する実施例６〜１０の抄紙用粘剤は、紙料凝集性、濾水性、紙の地合について優れ、発泡性が低減された抄紙用粘剤であった。
一方、ポリエチレンオキサイドのみからなる比較例４は、発泡性の点で劣っていた。
以上より明らかなように、実施例１〜１０の抄紙用粘剤は、比較例１〜４で得られた抄紙用粘剤と比較して、同量で紙料により高い分散性を付与することができ、良好な抄紙を実現させるものであり、かつ取り扱い性に優れたものであった。 As shown in Table 3, the papermaking adhesives of Examples 6 to 10 containing polyethylene oxide and the acrylamide copolymer of Example 2 are used for paper aggregation, drainage, and paper texture. It was an excellent paper adhesive with reduced foaming properties.
On the other hand, Comparative Example 4 consisting only of polyethylene oxide was inferior in terms of foamability.
As is clear from the above, the papermaking adhesives of Examples 1 to 10 give higher dispersibility to the paper stock in the same amount as compared with the papermaking adhesives obtained in Comparative Examples 1 to 4. It was possible to achieve good papermaking and excellent handleability.

本発明の抄紙用粘剤は、ポリエチレンオキサイド、ポリアクリルアミド、アニオン性アクリルアミド系重合体が増粘剤用途として使用されている産業に好適に用いることができ、特に、従来は一種類の抄紙用粘剤の適用が困難であったトイレットペーパー及びティッシュペーパー等の生産品目どうしにおいても、好適に汎用することができる。

The paper-making viscosity of the present invention can be suitably used in industries where polyethylene oxide, polyacrylamide, and anionic acrylamide polymers are used as thickener applications. It can be suitably used widely in production items such as toilet paper and tissue paper for which application of the agent is difficult.

Claims (4)

アクリルアミドに少なくともアニオン性基を有するビニル系単量体が共重合したアクリルアミド系共重合体を含み、
前記アクリルアミド系共重合体は前記ビニル系単量体単位を０．４〜１．５モル％含有し、前記アクリルアミド系共重合体が下記粘度条件を満たすことを特徴とする抄紙用粘剤。
（粘度条件）
アクリルアミド系共重合体と食塩４質量％とを含む食塩水溶液の粘度が、前記食塩水溶液と同じ濃度のアクリルアミド系共重合体の純水溶液の粘度より高いこと。 An acrylamide copolymer obtained by copolymerizing at least a vinyl monomer having an anionic group with acrylamide;
The acrylamide copolymer contains 0.4 to 1.5 mol% of the vinyl monomer unit, and the acrylamide copolymer satisfies the following viscosity condition.
(Viscosity condition)
The viscosity of a saline solution containing an acrylamide copolymer and 4% by mass of sodium chloride is higher than the viscosity of a pure aqueous solution of an acrylamide copolymer having the same concentration as the saline solution. 前記ビニル系単量体は、アクリル酸（塩）及び／又はアクリルアミド−２−メチルプロパンスルホン酸（塩）であることを特徴とする請求項１に記載の抄紙用粘剤。   2. The papermaking adhesive according to claim 1, wherein the vinyl monomer is acrylic acid (salt) and / or acrylamido-2-methylpropanesulfonic acid (salt). 前記アクリルアミド系共重合体１質量％を純水中に含む１質量％純水溶液の粘度が２０００ｍＰａ・ｓ以上であることを特徴とする請求項１ないし２のいずれかに記載の抄紙用粘剤。 Nebazai papermaking according to any one of claims 1 to 2, wherein the viscosity of 1 wt% pure aqueous solution containing the acrylamide copolymer 1 wt% in pure water is 2000 mPa · s or more. さらにポリエチレンオキサイドを含有し、前記アクリルアミド系共重合体が２０〜７５質量％、ポリエチレンオキサイドが２５〜８０質量％であることを特徴とする請求項１ないし３のいずれかに記載の抄紙用粘剤。 The papermaking adhesive according to any one of claims 1 to 3 , further comprising polyethylene oxide, wherein the acrylamide copolymer is 20 to 75% by mass and the polyethylene oxide is 25 to 80% by mass. .
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