JP2003221795A - Surface sizing agent and coated paper produced by using the same - Google Patents
Surface sizing agent and coated paper produced by using the sameInfo
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- JP2003221795A JP2003221795A JP2002018218A JP2002018218A JP2003221795A JP 2003221795 A JP2003221795 A JP 2003221795A JP 2002018218 A JP2002018218 A JP 2002018218A JP 2002018218 A JP2002018218 A JP 2002018218A JP 2003221795 A JP2003221795 A JP 2003221795A
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- water
- akd
- sizing agent
- surface sizing
- soluble
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アルキルケテンダ
イマー(以下、ＡＫＤという)の水性エマルションを単用
し、或は、当該ＡＫＤエマルションと水溶性共重合体を
併用した表面サイズ剤に関し、特に、２液併用型におい
ては、貯蔵安定性に優れ、酸性紙並びに中性紙のいずれ
においても優れたサイズ性を示し、塗工紙の摩擦係数の
低下も抑制できるものを提供する。TECHNICAL FIELD The present invention relates to a surface sizing agent in which an aqueous emulsion of an alkyl ketene dimer (hereinafter referred to as AKD) is used alone, or the AKD emulsion and a water-soluble copolymer are used in combination, and particularly, The two-liquid combination type is excellent in storage stability, exhibits excellent sizing property in both acidic paper and neutral paper, and can suppress a decrease in friction coefficient of coated paper.
【０００２】[0002]
【従来の技術】近年、酸性紙の劣化の問題、抄紙工程で
の白水のクローズド化、コート損紙の混入の問題、填料
として安価な炭酸カルシウムの利用などの観点から、中
性抄紙への要求が高まり、中性抄紙用のサイズ剤の需要
が増している。また、サイジング方法としては、パルプ
スラリーにサイズ剤を添加する内添サイジングと、抄紙
工程で得られた紙の表面にサイズ剤を塗工する表面サイ
ジングがあるが、後者に用いる表面サイズ剤は、内添サ
イズ剤に比べて抄紙用水の影響を受けにくく、歩留りが
高く、工程管理が行い易いなどの利点がある。2. Description of the Related Art In recent years, there has been a demand for neutral papermaking from the viewpoints of deterioration of acid paper, closure of white water in the papermaking process, mixing of coated broke, and use of inexpensive calcium carbonate as a filler. The demand for sizing agents for neutral papermaking is increasing. Further, as the sizing method, there are internal sizing for adding a sizing agent to the pulp slurry, and surface sizing for applying a sizing agent to the surface of the paper obtained in the papermaking process, but the surface sizing agent used for the latter is Compared to the internally added sizing agent, it is less affected by papermaking water, has a high yield, and has advantages such as easy process control.
【０００３】従来の表面サイズ剤としては、スチレン−
マレイン酸系共重合体、スチレン−(メタ)アクリル酸系
共重合体などの水溶性共重合体、或は、ＡＫＤなどがあ
る。上記スチレン−マレイン酸系共重合体は、硫酸バン
ドを多く使用した酸性紙では良好なサイズ性を発現する
が、中性紙、硫酸バンドの少ない新聞紙などではサイズ
性能は劣る。また、上記スチレン−(メタ)アクリル酸系
共重合体は、スチレン−マレイン酸系共重合体に比べて
中性紙に対するサイズ性能は良いが、上記ＡＫＤに比べ
るとそのレベルは低い。Conventional surface sizing agents include styrene-
Examples include water-soluble copolymers such as maleic acid-based copolymers and styrene- (meth) acrylic acid-based copolymers, or AKD. The styrene-maleic acid-based copolymer exhibits good sizing properties on acidic papers containing a large amount of sulfuric acid bands, but has poor size performance on neutral papers, newspapers with few sulfuric acid bands, and the like. Further, the styrene- (meth) acrylic acid-based copolymer has better size performance for neutral paper than the styrene-maleic acid-based copolymer, but its level is lower than that of the AKD.
【０００４】一方、上記ＡＫＤ系の表面サイズ剤は、中
性紙において優れたサイズ性を示すという特長がある反
面、塗工紙の摩擦係数を大きく低下させ(滑り易く)、機
械的安定性が劣り塗工機を汚損し易いという問題があ
る。このため、ＡＫＤと水溶性共重合体を併用すること
により、中性紙でのサイズ性能をＡＫＤで確保しなが
ら、水溶性共重合体で摩擦係数の低下を抑制しているの
が実情である。On the other hand, the above-mentioned AKD-based surface sizing agent has a feature of exhibiting excellent sizing property in neutral paper, but on the other hand, it greatly reduces the friction coefficient of coated paper (slippery) and has a mechanical stability. Inferiorly, there is a problem that the coating machine is easily soiled. Therefore, by using AKD and a water-soluble copolymer in combination, the water-soluble copolymer suppresses the reduction of the friction coefficient while ensuring the size performance of neutral paper with AKD. .
【０００５】上記ＡＫＤと水溶性共重合体を併用した表
面サイズ剤の従来技術としては、下記のものなどがあ
る。
(1)特開平１１−２１７７９５号公報（従来技術１）
(メタ)アクリルアミド系共重合体の存在下で、スチレ
ン、アルキル(メタ)アクリレートなどの疎水性単量体を
主成分として乳化重合した共重合体のエマルションと、
カチオンデンプンなどで分散したＡＫＤエマルションと
を混合したエマルション型の表面サイズ剤が開示されて
いる。The prior art of the surface sizing agent using the AKD and the water-soluble copolymer in combination includes the following. (1) Japanese Patent Laid-Open No. 11-217795 (Prior Art 1) A copolymer obtained by emulsion-polymerizing a hydrophobic monomer such as styrene or an alkyl (meth) acrylate as a main component in the presence of a (meth) acrylamide-based copolymer. A polymer emulsion,
An emulsion-type surface sizing agent in which an AKD emulsion dispersed with a cationic starch or the like is mixed is disclosed.
【０００６】(2)特開平７−１１９０８２号公報（従来
技術２）
カチオンデンプンなどで分散したＡＫＤエマルション
と、アニオン性高分子型分散剤及び／又は両性高分子型
分散剤とを混合した表面サイズ剤が開示されている。こ
の場合、上記アニオン性高分子型分散剤はスチレンなど
のビニル化合物と(メタ)アクリル酸などのアニオン性単
量体との共重合物塩などであり、上記両性高分子型分散
剤はビニル化合物とアニオン性単量体とジメチルアミノ
エチル(メタ)アクリレートなどのカチオン性単量体との
共重合物塩、或は、ビニル化合物とＮ−メタクリロイル
オキシエチル−Ｎ,Ｎ−ジメチルアンモニウム−Ｎ−メ
チルカルボキシベタインなどの両性単量体との共重合物
塩などである。(2) Japanese Unexamined Patent Publication No. 7-119082 (Prior Art 2) Surface size obtained by mixing an AKD emulsion dispersed with cationic starch and an anionic polymer type dispersant and / or an amphoteric polymer type dispersant. Agents are disclosed. In this case, the anionic polymer dispersant is a copolymer salt of a vinyl compound such as styrene and an anionic monomer such as (meth) acrylic acid, and the amphoteric polymer dispersant is a vinyl compound. And a salt of a copolymer of an anionic monomer and a cationic monomer such as dimethylaminoethyl (meth) acrylate, or a vinyl compound and N-methacryloyloxyethyl-N, N-dimethylammonium-N-methyl. Examples thereof include copolymer salts with amphoteric monomers such as carboxybetaine.
【０００７】[0007]
【発明が解決しようとする課題】ＡＫＤエマルションと
水溶性共重合体を併用するタイプの表面サイズ剤におい
ては、上述したように、水溶性共重合体がアルカリ塩水
溶液の形態をとるため、その混合系はアルカリを呈す
る。これにより、通常、ＡＫＤエマルションは水溶性共
重合体との相溶性が悪く、エマルションが壊れて凝集物
が発生し易い。このため、予め２液を混合して保存して
おくと、サイズ性能が顕著に低下してしまい、これを回
避するためには使用直前に２液を混合し、塗工する必要
があるが、２液を撹拌混合すると粕が発生して、やはり
サイズ性能の低下を起こす恐れがある。また、一般に、
塗工液には、紙の表面強度付与の見地から酸化デンプン
などの水溶性高分子化合物を添加しているが、通常、Ａ
ＫＤエマルションはこの酸化デンプンなどの他の塗工成
分との相溶性も悪い。これらの問題点は前記従来技術１
〜２においても依然として残り、なかでも、ＡＫＤエマ
ルションと水溶性共重合体との相溶性、特に、予め２液
を混合して保存する際の貯蔵安定性は未だ満足すべき水
準にはほど遠く、解決すべき課題は多いのである。In the surface sizing agent of the type in which the AKD emulsion and the water-soluble copolymer are used in combination, as described above, the water-soluble copolymer takes the form of an aqueous solution of an alkali salt, and thus the mixture thereof is used. The system exhibits alkalinity. As a result, the AKD emulsion usually has poor compatibility with the water-soluble copolymer, and the emulsion is liable to break and aggregates are easily generated. For this reason, if the two liquids are mixed and stored in advance, the size performance will be significantly reduced. To avoid this, it is necessary to mix and coat the two liquids immediately before use. When the two liquids are mixed with stirring, a cake may be generated, which may also cause deterioration in size performance. Also, in general,
A water-soluble polymer compound such as oxidized starch is added to the coating liquid from the viewpoint of imparting surface strength to the paper.
KD emulsions also have poor compatibility with other coating components such as oxidized starch. These problems are caused by the conventional technique 1 described above.
2 still remains, and among them, the compatibility between the AKD emulsion and the water-soluble copolymer, especially the storage stability when preliminarily mixing and storing the two liquids is far from a satisfactory level. There are many tasks to be done.
【０００８】本発明は、水溶性高分子化合物との併用適
性を具備したＡＫＤエマルションを開発するとともに、
貯蔵安定性やサイズ性などに優れたＡＫＤと水溶性共重
合体との２液混合型の表面サイズ剤を開発することを技
術的課題とする。The present invention develops an AKD emulsion which is suitable for use in combination with a water-soluble polymer compound.
The technical task is to develop a two-liquid mixed surface sizing agent of AKD and a water-soluble copolymer, which has excellent storage stability and sizing properties.
【０００９】[0009]
【課題を解決するための手段】本出願人は、先に、特開
昭６２−１５３９７号公報(以下、先行技術という)で、
ＡＫＤをカチオンデンプンなどで分散したＡＫＤエマル
ションにおいて、ＡＫＤやカチオンデンプンの粒子表面
を保護し、分散粒子を安定化させる目的で、硫酸アルミ
ニウム、塩化マグネシウムなどの水溶性金属塩をＡＫＤ
に対して金属塩として０.０５〜３重量％含有する内添
サイズ剤を開示した(同公報の特許請求の範囲、作用、
実施例の項目参照)。Means for Solving the Problems The applicant of the present invention has previously disclosed in Japanese Patent Laid-Open No. 62-15397 (hereinafter referred to as prior art),
In an AKD emulsion in which AKD is dispersed with cationic starch or the like, water-soluble metal salts such as aluminum sulfate and magnesium chloride are added to AKD emulsion for the purpose of protecting the particle surface of AKD and cationic starch and stabilizing the dispersed particles.
In contrast, an internally added sizing agent containing 0.05 to 3% by weight as a metal salt is disclosed (claims, action,
(Refer to the item of the example).
【００１０】本発明者は、上記先行技術を出発点とし
て、この内添サイズ剤の技術を表面サイズ剤に利用する
とともに、ＡＫＤエマルションの性状を特殊化すること
を鋭意研究した結果、カチオン電荷を特定範囲に抑制
し、且つ、上記内添サイズ剤で使用した水溶性金属塩を
転用的に添加したＡＫＤエマルションは、スチレン−
(メタ)アクリル酸系共重合体などの水溶性共重合体、或
は、酸化デンプンなどの水溶性高分子化合物に対して良
好な併用適性を具備すること、従って、この特殊化した
ＡＫＤエマルションを水溶性共重合体に混合すると良好
な相溶性を示し、貯蔵安定性や酸性紙〜中性紙でのサイ
ズ性に優れた表面サイズ剤を提供できることを見い出し
て、本発明を完成した。The inventors of the present invention have studied the above prior art as a starting point to utilize the technique of internally added sizing agent as a surface sizing agent and to specialize the properties of the AKD emulsion. The AKD emulsion, which is suppressed to a specific range and to which the water-soluble metal salt used in the internal sizing agent is diverted, is styrene-
It has good compatibility with water-soluble copolymers such as (meth) acrylic acid-based copolymers or water-soluble polymer compounds such as oxidized starch. Therefore, this specialized AKD emulsion is used. The present invention has been completed by finding that a surface sizing agent exhibiting good compatibility when mixed with a water-soluble copolymer and having excellent storage stability and sizing property on acidic paper to neutral paper can be provided.
【００１１】即ち、本発明１は、ＡＫＤをカチオン基含
有高分子化合物で水中に乳化分散し、水溶性金属塩を含
有して、ゼータ電位を−５〜＋２０ｍＶに調整したＡＫ
Ｄエマルションからなることを特徴とする水溶性高分子
化合物との併用適性を備えたＡＫＤ系表面サイズ剤であ
る。That is, the present invention 1 is an AK in which AKD is emulsified and dispersed in water with a cationic group-containing polymer compound and contains a water-soluble metal salt to adjust the zeta potential to -5 to +20 mV.
It is an AKD-based surface sizing agent having a suitability for use with a water-soluble polymer compound characterized by comprising a D emulsion.
【００１２】本発明２は、上記本発明１において、カチ
オン基含有高分子化合物がカチオン性又は両性の水溶性
高分子化合物であり、ＡＫＤに対して、カチオン基含有
高分子化合物を１０〜２５重量％含有することを特徴と
する水溶性高分子化合物との併用適性を備えたＡＫＤ系
表面サイズ剤である。The present invention 2 is the same as the above Invention 1, wherein the cation group-containing polymer compound is a cationic or amphoteric water-soluble polymer compound, and the cation group-containing polymer compound is contained in an amount of 10 to 25% by weight relative to AKD. % AKD-based surface sizing agent that is suitable for combined use with a water-soluble polymer compound.
【００１３】本発明３は、上記本発明１又は２におい
て、ＡＫＤに対して、水溶性金属塩を金属換算で０.０
０５〜２重量％含有することを特徴とする水溶性高分子
化合物との併用適性を備えたＡＫＤ系表面サイズ剤であ
る。The present invention 3 is the same as the above-mentioned invention 1 or 2, wherein the water-soluble metal salt is 0.0 in terms of metal with respect to AKD.
It is an AKD-based surface sizing agent which is suitable for combined use with a water-soluble polymer compound, characterized in that it is contained in an amount of 05 to 2 wt%.
【００１４】本発明４は、(Ａ)疎水性単量体とカルボン
酸基含有アニオン性単量体を反応させた酸価１５０〜３
５０mgKOH／gの水溶性共重合体と、(Ｂ)請求項１〜３の
いずれか１項のＡＫＤエマルションとを含有する表面サ
イズ剤である。The present invention 4 is (A) an acid value of 150 to 3 obtained by reacting a hydrophobic monomer with a carboxylic acid group-containing anionic monomer.
A surface sizing agent containing 50 mgKOH / g of a water-soluble copolymer and (B) the AKD emulsion according to any one of claims 1 to 3.
【００１５】本発明５は、上記本発明４において、水溶
性共重合体(Ａ)とＡＫＤエマルション(Ｂ)の混合割合
が、Ａ／Ｂ＝５０〜９９重量部／５０〜１重量部である
表面サイズ剤である。The present invention 5 is the same as the above invention 4, wherein the mixing ratio of the water-soluble copolymer (A) and the AKD emulsion (B) is A / B = 50 to 99 parts by weight / 50 to 1 part by weight. It is a surface sizing agent.
【００１６】本発明６は、上記本発明４又は５におい
て、疎水性単量体がスチレン類、(メタ)アクリル酸エス
テル類などであり、カルボン酸基含有アニオン性単量体
がアクリル酸、メタクリル酸、マレイン酸、イタコン酸
などである表面サイズ剤である。The present invention 6 is the same as the above invention 4 or 5, wherein the hydrophobic monomer is styrene, (meth) acrylic acid ester, and the carboxylic acid group-containing anionic monomer is acrylic acid or methacrylic acid. Surface sizing agents such as acids, maleic acid and itaconic acid.
【００１７】本発明７は、上記本発明４〜６のいずれか
において、水溶性共重合体(Ａ)が、スチレンとアクリル
酸、スチレンとアクリル酸とマレイン酸、又はスチレン
とマレイン酸を単量体組成とする共重合体であることを
特徴とする表面サイズ剤である。In a seventh aspect of the present invention according to any one of the fourth to sixth aspects, the water-soluble copolymer (A) comprises styrene and acrylic acid, styrene and acrylic acid and maleic acid, or styrene and maleic acid in a single amount. A surface sizing agent characterized by being a copolymer having a body composition.
【００１８】本発明８は、上記本発明１〜７のいずれか
の表面サイズ剤を塗工処理した紙である。The present invention 8 is a paper coated with the surface sizing agent according to any one of the above inventions 1 to 7.
【００１９】本発明９、上記本発明８において、さら
に、酸化デンプン、ポリビニルアルコールなどの表面強
度用水溶性高分子化合物を表面サイズ剤と共に塗工した
紙である。The present invention 9 and the above invention 8, further comprising paper coated with a water-soluble polymer compound for surface strength such as oxidized starch and polyvinyl alcohol together with a surface sizing agent.
【００２０】本発明１０は、上記本発明８又は９におい
て、紙が、硫酸バンド及び炭酸カルシウムの存在下で湿
式抄造した紙であることを特徴とする紙である。A tenth aspect of the present invention is the paper according to the eighth or ninth aspect of the invention, characterized in that the paper is wet papermaking in the presence of a sulfuric acid band and calcium carbonate.
【００２１】[0021]
【発明の実施の形態】本発明は、第一に、水溶性金属塩
を含有し、ゼータ電位を特定範囲に調整したＡＫＤエマ
ルションからなる表面サイズ剤であり、第二に、このＡ
ＫＤエマルションと特定の酸価を有する水溶性共重合体
とを併用する表面サイズ剤であり、第三に、これらの表
面サイズ剤を塗工した紙である。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is, firstly, a surface sizing agent comprising an AKD emulsion containing a water-soluble metal salt and having a zeta potential adjusted to a specific range.
A surface sizing agent in which a KD emulsion and a water-soluble copolymer having a specific acid value are used in combination, and thirdly, paper coated with these surface sizing agents.
【００２２】本発明１のＡＫＤエマルションは、ＡＫＤ
をカチオン基含有高分子化合物で水中に乳化分散し、水
溶性金属塩を含有させたものである。上記ＡＫＤは下記
の一般式(イ)で表される化合物であり、狭義のアルキル
ケテンダイマーに限らず、その類似化合物までを含む広
義のアルキルケテンダイマー系化合物を意味する。The AKD emulsion of the present invention 1 is AKD emulsion
Is emulsified and dispersed in water with a cationic group-containing polymer compound to contain a water-soluble metal salt. The above AKD is a compound represented by the following general formula (a), and means not only an alkylketene dimer in a narrow sense but also an alkylketene dimer compound in a broad sense including a similar compound.
【化１】
（式(イ)中、Ｒ1及びＲ2はＣ8〜Ｃ30の同一又は異なる
炭化水素基である。）上記一般式(イ)において、Ｒ1又
はＲ2の炭化水素基は、例えば、オクチル、デシル、ド
デシル、テトラデシル、ヘキサデシル、オクタデシル、
エイコシル等のアルキル基、オクテニル、デセニル、ド
デセニル、テトラデセニル、ヘキサデセニル、オクタデ
セニル、エイコセニル等のアルケニル基、オクチルフェ
ニル、ノニルフェニル、ドデシルフェニル等の置換フェ
ニル基、ノニルシクロヘキシル等の置換シクロアルキル
基、フェニルエチル等のアラルキル基などであり、Ｃ10
〜Ｃ25が好ましい。そこで、上記ＡＫＤの具体例を挙げ
ると、オクタデシルケテンダイマー、ヘキサデシルケテ
ンダイマー、テトラデシルケテンダイマー、ドデシルケ
テンダイマーなどであり、また、天然脂肪酸混合物から
合成されたケテンダイマーも有効である。これらの列記
化合物、或は他種のＡＫＤは単用又は併用できることは
いうまでもない。[Chemical 1] (In the formula (a), R 1 and R 2 are the same or different hydrocarbon groups of C 8 to C 30. ) In the above general formula (a), the hydrocarbon group of R 1 or R 2 is, for example, Octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl,
Alkyl groups such as eicosyl, alkenyl groups such as octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, substituted phenyl groups such as octylphenyl, nonylphenyl, dodecylphenyl, substituted cycloalkyl groups such as nonylcyclohexyl, phenylethyl, etc. Aralkyl groups such as C 10
~C 25 is preferred. Therefore, specific examples of the AKD include octadecyl ketene dimer, hexadecyl ketene dimer, tetradecyl ketene dimer, dodecyl ketene dimer, and ketene dimer synthesized from a natural fatty acid mixture is also effective. It goes without saying that these listed compounds or other types of AKD can be used alone or in combination.
【００２３】上記ＡＫＤを水中に乳化分散するカチオン
基含有高分子化合物は、カチオン性又は両性の水溶性高
分子化合物が好ましく、前者のカチオン性高分子化合物
としては、カチオンデンプン、或は適正なカチオン度を
有する合成高分子化合物などが挙げられる。また、後者
の両性高分子化合物は、基本的に、両性デンプンを初
め、ビニル基含有単量体とアニオン性単量体とカチオン
性単量体、或は、ビニル基含有単量体と両性単量体を反
応させた共重合体などであり、具体的には、(メタ)アク
リルアミド系共重合体などが挙げられる。また、カチオ
ンデンプンとアニオン性重合体の混合物のように、１種
以上の水溶性高分子を含有した両性高分子化合物でも良
い。但し、両性の高分子化合物の場合には、カチオン性
過剰の組成に調整される。本発明２に示すように、上記
カチオン基含有高分子化合物の含有率は、ＡＫＤに対し
て１０〜２５重量％程度が好ましく、１５〜２０重量％
がより好ましい。また、このカチオン基含有高分子化合
物としてはカチオンデンプンがより有効である。尚、Ａ
ＫＤの乳化分散に際しては、このカチオン基含有高分子
化合物の外に、ナフタレンスルホン酸塩のホルマリン縮
合物、リグニンスルホン酸塩、グリセリン脂肪酸エステ
ル、ソルビタン脂肪酸エステル、ショ糖脂肪酸エステル
などの公知の分散剤を併用できることはいうまでもな
い。The cationic group-containing polymer compound for emulsifying and dispersing AKD in water is preferably a cationic or amphoteric water-soluble polymer compound, and the former cationic polymer compound is a cationic starch or a suitable cation. And synthetic polymer compounds having a certain degree. In addition, the latter amphoteric polymer basically includes amphoteric starch, vinyl group-containing monomer, anionic monomer and cationic monomer, or vinyl group-containing monomer and amphoteric monomer. Examples thereof include copolymers obtained by reacting a monomer, and specific examples thereof include (meth) acrylamide copolymers. It may also be an amphoteric polymer compound containing one or more water-soluble polymers, such as a mixture of cationic starch and anionic polymer. However, in the case of an amphoteric polymer compound, the composition is adjusted to have a cationic excess. As shown in the present invention 2, the content of the above cationic group-containing polymer compound is preferably about 10 to 25% by weight, preferably 15 to 20% by weight, based on AKD.
Is more preferable. Moreover, cationic starch is more effective as the cationic group-containing polymer compound. Incidentally, A
In emulsifying and dispersing KD, in addition to the cationic group-containing polymer compound, known dispersants such as formalin condensate of naphthalene sulfonate, lignin sulfonate, glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester. Needless to say, can be used in combination.
【００２４】上記水溶性金属塩は、ＡＫＤの分散粒子の
安定化とＡＫＤのセルロース繊維への定着促進化などを
目的として含有され、マグネシウム、アルミニウム、亜
鉛及び鉄よりなる群から選ばれた金属の少なくとも一種
と、硫酸、塩酸、硝酸、ギ酸、酢酸、クロル酢酸、グル
コン酸、グリコール酸などの低級脂肪酸よりなる群から
選ばれた酸の少なくとも一種との水溶性塩をいう。当該
水溶性金属塩の具体例は、硫酸アルミニウム、塩化マグ
ネシウム、塩化アルミニウムなどであり、硫酸アルミニ
ウムが好ましい。また、本発明３に示すように、この水
溶性金属塩の含有率はＡＫＤに対して金属換算で０.０
０５〜２重量％程度であるが、好ましくは０.０１〜０.
５重量％、より好ましくは０.０５〜０.３重量％であ
る。The above water-soluble metal salt is contained for the purpose of stabilizing dispersed particles of AKD and accelerating the fixing of AKD to the cellulose fiber, and is a metal selected from the group consisting of magnesium, aluminum, zinc and iron. It means a water-soluble salt of at least one kind and at least one kind of acid selected from the group consisting of lower fatty acids such as sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid, chloroacetic acid, gluconic acid and glycolic acid. Specific examples of the water-soluble metal salt include aluminum sulfate, magnesium chloride, aluminum chloride and the like, and aluminum sulfate is preferable. Further, as shown in the present invention 3, the content of the water-soluble metal salt is 0.0 in terms of metal relative to AKD.
It is about 05 to 2% by weight, but preferably 0.01 to 0.
It is 5% by weight, more preferably 0.05 to 0.3% by weight.
【００２５】上記ＡＫＤエマルションのゼータ電位は−
５〜＋２０ｍＶに調整され、カチオン電荷を抑制してあ
る。これにより、表面サイズ剤として使用されるスチレ
ン−マレイン酸系共重合体などの水溶性共重合体や、酸
化デンプンなどの他の塗工成分との相溶性が円滑に改善
され、これらの水溶性高分子化合物との併用適性を具備
する。上記カチオン基含有高分子化合物で乳化分散され
たＡＫＤエマルションは、同時に添加される分散剤(例
えば、ナフタレンスルホン酸塩のホルマリン縮合物な
ど)により若干マイスナ側に傾く場合もあるが、アニオ
ン帯電である繊維への定着性の見地からゼータ電位の下
限は−５ｍＶであり、逆に、上限が＋２０ｍＶを越える
と、アルカリ塩水溶液の形態をとる水溶性共重合体など
との相溶性が損なわれる。ＡＫＤエマルションのゼータ
電位は＋５〜＋１５ｍＶ程度が好ましく、＋１０ｍＶ前
後がより好ましい。The zeta potential of the above AKD emulsion is −
It is adjusted to 5 to +20 mV to suppress the cation charge. As a result, compatibility with water-soluble copolymers such as styrene-maleic acid-based copolymers used as a surface sizing agent and other coating components such as oxidized starch is smoothly improved, and these water-soluble copolymers are dissolved. It is suitable for use in combination with a polymer compound. The AKD emulsion emulsified and dispersed with the above cationic group-containing polymer compound may be slightly anion-charged due to a dispersant added at the same time (for example, a formalin condensate of naphthalene sulfonate), but it is anionically charged. The lower limit of the zeta potential is −5 mV from the viewpoint of the fixability to the fiber, and conversely, when the upper limit exceeds +20 mV, the compatibility with a water-soluble copolymer in the form of an aqueous solution of an alkali salt is impaired. The zeta potential of the AKD emulsion is preferably +5 to +15 mV, more preferably around +10 mV.
【００２６】本発明４は、上記ＡＫＤエマルションに水
溶性共重合体を併用した２液混合型の表面サイズ剤であ
る。上記水溶性共重合体は、疎水性単量体とカルボン酸
基含有アニオン性単量体とを反応させて、酸価１５０〜
３５０mgKOH／gに調整された共重合体である。本発明６
に示すように、上記疎水性単量体としては、スチレン
類、(メタ)アクリル酸系エステル類などが挙げられる。
上記スチレン類には、スチレンを初め、α−メチルスチ
レンなどのビニル基に置換基を有するスチレン類、或
は、ビニルトルエン、ｐ−クロルスチレンなどのベンゼ
ン環に置換基を有するスチレン類などを単用又は併用で
きる。上記(メタ)アクリル酸系エステル類は、メタクリ
ル酸メチル、メタクリル酸エチル、メタクリル酸プロピ
ル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチ
ル、メタクリル酸ｔ−ブチル、メタクリル酸シクロヘキ
シル、メタクリル酸ベンジルなどのメタクリル酸エステ
ル類、アクリル酸エチル、アクリル酸プロピル、アクリ
ル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｔ
−ブチル、アクリル酸シクロヘキシル、アクリル酸ベン
ジルなどのアクリル酸エステル類などである。上記カル
ボン酸基含有アニオン性単量体としては、カルボキシル
基を少なくとも１個有するアニオン性の不飽和単量体で
あり、アクリル酸、メタクリル酸、クロトン酸、(無水)
マレイン酸、フマル酸、イタコン酸、(無水)シトラコン
酸、或はこれらの塩などを単用又は併用できる。The present invention 4 is a two-liquid mixed type surface sizing agent in which a water-soluble copolymer is used in combination with the AKD emulsion. The water-soluble copolymer is obtained by reacting a hydrophobic monomer with a carboxylic acid group-containing anionic monomer to give an acid value of 150 to
It is a copolymer adjusted to 350 mgKOH / g. Invention 6
As shown in, the hydrophobic monomer includes styrenes, (meth) acrylic acid esters, and the like.
Examples of the styrenes include styrene, styrenes having a substituent on the vinyl group such as α-methylstyrene, and styrenes having a substituent on the benzene ring such as vinyltoluene and p-chlorostyrene. Can be used together. The above-mentioned (meth) acrylic acid-based esters are methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate. Esters, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t acrylate
-Acrylic acid esters such as butyl, cyclohexyl acrylate, and benzyl acrylate. The carboxylic acid group-containing anionic monomer is an anionic unsaturated monomer having at least one carboxyl group, acrylic acid, methacrylic acid, crotonic acid, (anhydrous)
Maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid, or salts thereof may be used alone or in combination.
【００２７】上記２液混合型の表面サイズ剤に用いる水
溶性共重合体は、本発明７に示すように、スチレンと
(メタ)アクリル酸、スチレンと(メタ)アクリル酸とマレ
イン酸、或は、スチレンとマレイン酸を各単量体組成と
する共重合体が好ましい。特に、マレイン酸は不飽和２
塩基酸なので、(メタ)アクリル酸などの１塩基酸に比べ
て単位重量当たりに導入できるアニオン性基がより多く
なるので、ＡＫＤエマルションの安定に寄与する。上記
疎水性単量体とアニオン性単量体の重合で得られる水溶
性共重合体の酸価は１５０〜３５０mgKOH／gであり、好
ましくは１８０〜３００mgKOH／gである。酸価が１５０
mgKOH／gより低いと共重合体のケン化時の水溶性が低下
し、また、疎水性の増大により溶液に濁りが生じて均一
塗工に支障を来す。逆に、３５０mgKOH／gを越えると水
溶性基の増大により撥水性が低減し、サイズ性能の低下
を来す。The water-soluble copolymer used in the above-mentioned two-component mixed surface sizing agent is, as shown in the present invention 7, styrene and
A copolymer having (meth) acrylic acid, styrene, (meth) acrylic acid and maleic acid, or a copolymer having styrene and maleic acid as respective monomer compositions is preferable. In particular, maleic acid is unsaturated 2
Since it is a basic acid, more anionic groups can be introduced per unit weight than monobasic acids such as (meth) acrylic acid, which contributes to the stability of the AKD emulsion. The acid value of the water-soluble copolymer obtained by polymerizing the above hydrophobic monomer and anionic monomer is 150 to 350 mgKOH / g, preferably 180 to 300 mgKOH / g. Acid value is 150
If it is lower than mgKOH / g, the water solubility of the copolymer during saponification will decrease, and the increased hydrophobicity will cause turbidity in the solution, hindering uniform coating. On the other hand, when it exceeds 350 mgKOH / g, the water repellency is reduced due to the increase of water-soluble groups, and the size performance is deteriorated.
【００２８】上記水溶性共重合体は、前記疎水性単量体
とアニオン性単量体の混合物を重合開始剤の存在下に溶
液重合、乳化重合、その他、常法の重合反応によって得
られ、好ましくは公知の水系溶液重合又は乳化重合で製
造される。上記溶液重合又は乳化重合に際しては、基本
的に乳化剤を混合した水系に、各種の単量体成分を混合
物にして一括添加するか、又は徐々に添加する。上記乳
化剤には公知のアニオン性、ノニオン性、又は両性界面
活性剤などを使用することができる。上記アニオン性界
面活性剤としては、ドデシルベンゼンスルホン酸ナトリ
ウムなどのアルキルベンゼンスルホン酸塩、脂肪酸塩、
ロジン酸塩、アルキル硫酸エステル、アルキルスルホコ
ハク酸塩、α−オレフィンスルホン酸塩、アルキルナフ
タレンスルホン酸塩、ポリオキシエチレンアルキル(ア
リール)硫酸エステル塩などが挙げられる。上記ノニオ
ン性界面活性剤としては、Ｃ1〜Ｃ20アルカノール、フ
ェノール、ナフトール、ビスフェノール類、Ｃ1〜Ｃ20
アルキルナフトール、ポリオキシエチレン(プロピレン)
グリコール、脂肪族アミンなどのエチレンオキシド及び
／又はプロピレンオキシド付加物などが挙げられる。上
記両性界面活性剤としては、カルボキシベタイン型、ス
ルホベタイン型、アミノカルボン酸型、イミダゾリン誘
導型などの界面活性剤が挙げられる。The above water-soluble copolymer is obtained by subjecting a mixture of the above-mentioned hydrophobic monomer and anionic monomer to solution polymerization in the presence of a polymerization initiator, emulsion polymerization, or other conventional polymerization reaction. It is preferably produced by known aqueous solution polymerization or emulsion polymerization. In the solution polymerization or emulsion polymerization, basically, various monomer components are mixed and added all at once to an aqueous system mixed with an emulsifier, or gradually added. As the emulsifier, a known anionic, nonionic or amphoteric surfactant or the like can be used. As the anionic surfactant, an alkylbenzene sulfonate such as sodium dodecylbenzenesulfonate, a fatty acid salt,
Examples thereof include rosin acid salts, alkyl sulfates, alkyl sulfosuccinates, α-olefin sulfonates, alkylnaphthalene sulfonates, and polyoxyethylene alkyl (aryl) sulfate ester salts. Examples of the nonionic surfactants include C 1 to C 20 alkanols, phenols, naphthols, bisphenols, C 1 to C 20.
Alkylnaphthol, polyoxyethylene (propylene)
Examples thereof include ethylene oxide and / or propylene oxide adducts such as glycols and aliphatic amines. Examples of the amphoteric surfactant include carboxybetaine-type, sulfobetaine-type, aminocarboxylic acid-type, and imidazoline-derivative type surfactants.
【００２９】上記重合開始剤としては、過硫酸アンモニ
ウム、過硫酸カリウム、過硫酸ナトリウムなどの過硫酸
塩、又は２,２−アゾビス−Ｎ−２−カルボキシエチル
−２−メチルプロピオンアミジンハイドレ−トなどの水
溶性アゾ系化合物、又は過酸化ベンゾイルなどの油溶性
開始剤などが挙げられる。また、上記乳化重合に際して
は、分子量を調整する目的で連鎖移動剤を使用できるこ
とはいうまでもない。連鎖移動剤としては、ｎ−ドデシ
ルメルカプタン、ｎ−オクチルメルカプタン、メルカプ
トエタノール、チオグリコール酸及びその塩、チオグリ
コール酸ブチル等のチオグリコール酸エステルなどのメ
ルカプタン類、イソプロピルアルコール、四塩化炭素、
クメンなどを単用又は併用できる。Examples of the above-mentioned polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, and 2,2-azobis-N-2-carboxyethyl-2-methylpropionamidine hydrate. Examples thereof include water-soluble azo compounds and oil-soluble initiators such as benzoyl peroxide. It goes without saying that a chain transfer agent can be used for the purpose of adjusting the molecular weight in the emulsion polymerization. As the chain transfer agent, n-dodecyl mercaptan, n-octyl mercaptan, mercaptoethanol, thioglycolic acid and its salts, mercaptans such as thioglycolic acid ester such as butyl thioglycolate, isopropyl alcohol, carbon tetrachloride,
Cumene etc. can be used alone or in combination.
【００３０】上述の重合反応を終了した共重合体は、水
酸化ナトリウム、水酸化カリウム、アンモニア、低級ア
ミン、或はアルカノールアミンなどのアルカリで中和し
て、部分又は完全ケン化物(即ち、共重合体塩水溶液)と
する。この共重合体のケン化物は前記ＡＫＤエマルショ
ンと混合して、２液併用型の表面サイズ剤として使用さ
れる。The copolymer which has completed the above-mentioned polymerization reaction is neutralized with an alkali such as sodium hydroxide, potassium hydroxide, ammonia, lower amine, or alkanolamine to give a partially or completely saponified product (that is, copolymer). Polymer salt aqueous solution). The saponified product of this copolymer is mixed with the AKD emulsion to be used as a two-liquid combined type surface sizing agent.
【００３１】上記水溶性共重合体(Ａ)と前記ＡＫＤエマ
ルション(Ｂ)は、水溶性共重合体(Ａ)が共重合体塩水溶
液であることを基準として、本発明５に示すように、Ａ
／Ｂ＝５０〜９９重量部／５０〜１重量部の割合で混合
される。好ましくは、Ａ／Ｂ＝７０〜９０重量部／３０
〜１０重量部であり、より好ましくはＡ／Ｂ＝７５重量
部／２５重量部の前後である。以上のように、２液混合
型の表面サイズ剤においては、相溶性の確保、塗工紙の
摩擦係数の低下防止、酸性紙〜中性紙でのサイズ性の発
現などの総合的な見地から、水溶性共重合体とＡＫＤを
均等な重量比、或は、これより水溶性共重合体が多い割
合(概ね、水溶性共重合体が主、ＡＫＤが従の割合)で混
合するのが有効である。但し、上記(Ｂ)成分を(Ａ)成分
より多く配合することもでき、この場合には、中性サイ
ズ性をより有効に向上できる。この２液混合型の表面サ
イズ剤の調製方法としては、塗工直前に２液を混合して
も良いが、２液は相溶性に優れ、粕が発生したり凝集の
恐れはないため、予め混合液の形態で貯蔵しておいて
も、サイズ性能が低下する恐れはない。As shown in the present invention 5, the water-soluble copolymer (A) and the AKD emulsion (B) are based on the fact that the water-soluble copolymer (A) is an aqueous solution of a copolymer salt. A
/ B = 50 to 99 parts by weight / 50 to 1 parts by weight. Preferably, A / B = 70 to 90 parts by weight / 30
10 to 10 parts by weight, more preferably around A / B = 75 parts by weight / 25 parts by weight. As described above, in the two-liquid mixed surface sizing agent, from the comprehensive viewpoint of ensuring compatibility, preventing reduction of the friction coefficient of coated paper, and exhibiting sizing property in acidic paper to neutral paper. It is effective to mix the water-soluble copolymer and AKD in a uniform weight ratio or in a ratio in which the water-soluble copolymer is larger than this (generally, the water-soluble copolymer is the main and the AKD is the second). Is. However, the component (B) may be blended more than the component (A), and in this case, the neutral sizing property can be more effectively improved. As a method for preparing the two-liquid mixed type surface sizing agent, the two liquids may be mixed immediately before coating, but the two liquids are excellent in compatibility and there is no fear of generation of meal or aggregation, Even if it is stored in the form of a mixed solution, there is no risk that the size performance will deteriorate.
【００３２】本発明８は、ＡＫＤエマルションからなる
表面サイズ剤、或は、上記２液混合型の表面サイズ剤を
塗工した紙である。上記紙を構成するパルプ繊維は、製
紙用に通常使用されるＮＢＫＰ、ＬＢＫＰ等の木材パル
プなどの外、リンターパルプ、麻、バガス、ケナフ、エ
スパルト草、ワラ等の非木材パルプ、レーヨン、アセテ
ート等の半合成繊維、或は、ポリオレフィン、ポリアミ
ド、ポリエステル等の合成繊維などである。また、新聞
古紙、雑誌古紙、段ボール古紙、脱墨古紙などの古紙パ
ルプであっても良い。一方、紙には、湿式抄紙工程で、
填料、内添サイズ剤、染料、紙力増強剤、歩留り向上
剤、消泡剤などを必要に応じて添加できることはいうま
でもない。填料としては、重質及び軽質炭酸カルシウ
ム、クレー、タルク、酸化チタンなどが挙げられる。内
添サイズ剤としては、酸性又は中性抄紙用の各種ロジン
系サイズ剤、中性抄紙用のＡＫＤ系サイズ剤又はアルケ
ニルコハク酸無水物系サイズ剤などが挙げられ、酸性ロ
ジン系サイズ剤の定着には硫酸バンドが、ＡＫＤなどの
反応性サイズ剤にはカチオン系定着助剤が使用される。
冒述したように、近年は環境保全、酸性紙の劣化などの
観点から中性化指向が高まっているが、この中性抄紙に
おいては、安価な炭酸カルシウムが使用でき(パルプス
ラリーに対して５重量％以上が好ましい)、また、本発
明の表面サイズ剤のサイズ効果を促進する目的で、硫酸
バンドをパルプスラリーに対して０.５重量％以上添加
するのが好ましい。特に、２液混合型の表面サイズ剤を
中性紙などに塗工する際には、中性紙、或は硫酸バンド
量の少ない紙ではサイズ効果を発揮しにくい水溶性共重
合体の割合が多く、中性紙でのサイズ効果に優れたＡＫ
Ｄが少ない場合に、パルプスラリーへの硫酸バンドの添
加は有効である。The present invention 8 is a paper coated with the surface sizing agent comprising an AKD emulsion or the surface sizing agent of the above-mentioned two-liquid mixture type. The pulp fibers constituting the above-mentioned paper include not only wood pulp such as NBKP and LBKP usually used for papermaking but also non-wood pulp such as linter pulp, hemp, bagasse, kenaf, esparto grass and straw, rayon, acetate and the like. The semi-synthetic fibers, or synthetic fibers such as polyolefin, polyamide and polyester. Further, it may be used paper pulp such as used newspaper, used magazine, used corrugated paper, and used deinked paper. On the other hand, for paper, in the wet papermaking process,
It goes without saying that a filler, an internally added sizing agent, a dye, a paper strength enhancer, a retention improver, an antifoaming agent and the like can be added if necessary. Examples of the filler include heavy and light calcium carbonate, clay, talc, titanium oxide and the like. Examples of the internally added sizing agent include various rosin-based sizing agents for acidic or neutral papermaking, AKD-based sizing agents for neutral papermaking, and alkenylsuccinic anhydride-based sizing agents. A sulfuric acid band is used for the above, and a cationic fixing aid is used for the reactive sizing agent such as AKD.
As mentioned above, in recent years, the tendency toward neutralization has been increasing from the viewpoint of environmental protection, deterioration of acidic paper, etc. In this neutral papermaking, inexpensive calcium carbonate can be used (5% for pulp slurry). It is preferable to add 0.5% by weight or more to the pulp slurry for the purpose of promoting the size effect of the surface sizing agent of the present invention. In particular, when a two-liquid mixed surface sizing agent is applied to neutral paper or the like, the proportion of the water-soluble copolymer that is difficult to exert the size effect on neutral paper or paper with a small amount of sulfuric acid band is Many, AK with excellent size effect on neutral paper
When the D is low, the addition of the sulfuric acid band to the pulp slurry is effective.
【００３３】表面サイズ剤の塗工に際しては、紙の表面
強度向上などの見地から、酸化デンプン、リン酸エステ
ル化デンプン、カチオンデンプン、変性デンプンなどの
デンプン類、カルボキシメチルセルロースなどのセルロ
ース類、ポリビニルアルコール類、ポリアクリルアミド
類、アルギン酸塩などの水溶性高分子化合物を併用塗工
できることは勿論である。また、他の表面サイズ剤、防
腐剤、防滑剤、防錆剤、消泡剤、粘度調整剤、染料、顔
料などを併用しても良い。In applying the surface sizing agent, from the viewpoint of improving the surface strength of paper, starches such as oxidized starch, phosphoric esterified starch, cationic starch, modified starch, celluloses such as carboxymethyl cellulose, polyvinyl alcohol, etc. It goes without saying that water-soluble polymer compounds such as compounds, polyacrylamides and alginates can be used in combination. Further, other surface sizing agents, antiseptics, antislip agents, antirust agents, defoaming agents, viscosity modifiers, dyes, pigments and the like may be used in combination.
【００３４】本発明の紙は、電子写真用紙、インクジェ
ット用紙等の印刷・筆記・図画用紙、新聞紙、包装用
紙、薄葉紙、雑種紙などの通常の薄紙を初め、板紙、厚
紙などを含む広い概念である。表面サイズ剤を紙に塗工
する方法は、塗工機を用いた塗布を基本とするが、スプ
レーを用いた噴霧、紙を表面サイズ剤の処理液に浸漬す
る含浸などであっても良い。塗布機としては、サイズプ
レス、フィルムプレス、ゲートロールコーター、ブレー
ドコーター、キャレンダー、バーコーター、ナイフコー
ター、エアナイフコーターなどの公知のものが使用でき
る。また、一連の抄紙工程において、オンマシンコーテ
ィングとオフマシンコーティングのいずれで塗工しても
良い。本発明の表面サイズ剤の塗工量は、サイズ性の良
好な発現及び経済性などの見地から固形分換算で０.０
０５〜５ｇ／ｍ2であり、好ましくは０.０１〜０.５ｇ
／ｍ2である。The paper of the present invention is a broad concept including ordinary thin paper such as electrophotographic paper, ink jet paper, printing / writing / drawing paper, newspaper, wrapping paper, thin paper, hybrid paper, etc., and board, cardboard, etc. is there. The method of applying the surface sizing agent to the paper is basically application using a coating machine, but spraying using a spray, impregnation in which the paper is dipped in a treatment solution of the surface sizing agent, or the like may be used. As the coating machine, known ones such as a size press, a film press, a gate roll coater, a blade coater, a calender, a bar coater, a knife coater and an air knife coater can be used. Further, in a series of paper making steps, the coating may be performed by either on-machine coating or off-machine coating. The coating amount of the surface sizing agent of the present invention is 0.0 in terms of solid content in terms of good expression of sizing property and economy.
05-5 g / m 2 , preferably 0.01-0.5 g
/ M 2 .
【００３５】[0035]
【発明の効果】(1)水溶性共重合体のケン化物とＡＫＤ
エマルションを併用する従来の２液混合型の表面サイズ
剤は、混合系のアルカリにより分散粒子が壊れて凝集物
が発生し易いが、本発明の表面サイズ剤は、水溶性金属
塩を含有し、特定のゼータ電位でカチオン電荷を抑えた
特殊なＡＫＤエマルションを水溶性共重合体と併用する
ので、相溶性が良好で貯蔵安定性に優れる。従って、塗
工直前に２液を併用しても良いが、予め２液を混合して
貯蔵しておいても品質は安定であり、サイズ性能の低下
はない。また、２液の優れた相溶性により、機械的安定
性も良く、塗工直前に２液を撹拌混合しても粕の発生は
なく、サイズ性能を良好に発現できる。EFFECTS OF THE INVENTION (1) Saponified product of water-soluble copolymer and AKD
In the conventional two-liquid mixed type surface sizing agent that uses an emulsion together, the dispersed particles are easily broken by the alkali of the mixed system to generate aggregates, but the surface sizing agent of the present invention contains a water-soluble metal salt, Since a special AKD emulsion in which the cationic charge is suppressed at a specific zeta potential is used in combination with the water-soluble copolymer, the compatibility is good and the storage stability is excellent. Therefore, the two liquids may be used together immediately before coating, but the quality is stable and the size performance does not deteriorate even if the two liquids are mixed and stored in advance. Further, due to the excellent compatibility of the two liquids, the mechanical stability is also good, and even if the two liquids are stirred and mixed immediately before coating, no lees are generated and the size performance can be well expressed.
【００３６】(2)本発明の２液混合型表面サイズ剤で
は、中性紙や硫酸バンド内添量の少ない新聞紙などでサ
イズ性が発現しにくい水溶性共重合体の特性をＡＫＤエ
マルションで補強し、中性紙〜酸性紙でのサイズ性を良
好に改善できる。特に、本発明１０に示すように、酸性
抄紙に限らず、中性抄紙に際しても硫酸バンドを少量添
加すると、中性紙などでのサイズ効果が発現しにくい水
溶性共重合体の配合率が多く、中性紙でのサイズ効果に
優れたＡＫＤが少ない場合でも、この硫酸バンドの配合
により、中性紙でのサイズ性の発現を良好に担保するこ
とができる。(2) In the two-liquid mixed surface sizing agent of the present invention, the characteristics of the water-soluble copolymer, which is difficult to exhibit sizing property in neutral paper or newspaper with a small amount of sulfuric acid band internally added, are reinforced with an AKD emulsion. However, the size of the neutral paper to the acidic paper can be improved satisfactorily. In particular, as shown in the present invention 10, when a small amount of a sulfuric acid band is added not only to acidic papermaking but also to neutral papermaking, the blending ratio of the water-soluble copolymer, which hardly causes the size effect in neutral paper, is large. Even if the AKD, which has an excellent size effect on the neutral paper, is small, the sizing property of the neutral paper can be satisfactorily ensured by blending the sulfuric acid band.
【００３７】(3)本発明の２液混合型表面サイズ剤で
は、ＡＫＤによる塗工紙の摩擦係数の低下を水溶性共重
合体の併用によって抑制できるため、塗工紙の摩擦係数
が低下する問題を解消できる。(3) In the two-liquid mixed surface sizing agent of the present invention, the decrease in the friction coefficient of the coated paper due to AKD can be suppressed by the combined use of the water-soluble copolymer, so that the friction coefficient of the coated paper decreases. You can solve the problem.
【００３８】(4)本発明のＡＫＤエマルションは水溶性
金属塩を含み、カチオン電荷を適正に抑制しているた
め、酸化デンプンなどの他の塗工成分との相溶性も良
い。従って、表面サイズ剤としてこのＡＫＤエマルショ
ンを単用しても、或は、水溶性共重合体と併用しても、
塗工液の調製に際して粕の発生はなく、円滑な塗工処理
が図れる。(4) Since the AKD emulsion of the present invention contains a water-soluble metal salt and appropriately suppresses cationic charges, it has good compatibility with other coating components such as oxidized starch. Therefore, even if this AKD emulsion is used alone as the surface sizing agent, or in combination with the water-soluble copolymer,
No lees are generated during the preparation of the coating liquid, and a smooth coating process can be achieved.
【００３９】(5)本発明のＡＫＤエマルションを表面サ
イズとして単用する場合、当該エマルションは機械的安
定性、或は保存安定性に優れるため、塗工直前の使用に
限らず、予め調製・保存しておいてもサイズ性能の低下
はない。(5) When the AKD emulsion of the present invention is used alone as the surface size, the emulsion is excellent in mechanical stability or storage stability, so that it is not limited to use immediately before coating but is prepared and stored in advance. Even if you do, there is no reduction in size performance.
【００４０】以下、本発明の水溶性共重合体の合成例、
ＡＫＤエマルションの製造例、ＡＫＤエマルションの貯
蔵安定性、機械安定性などの各種評価試験例、水溶性共
重合体とＡＫＤエマルションを併用した２液混合型の表
面サイズ剤の製造実施例、この２液混合型の表面サイズ
剤の貯蔵安定性、塗工紙のサイズ性、紙滑り性などの各
種評価試験例を順次説明する。下記の合成例、製造例、
実施例、試験例中の「％」、「部」は基本的に重量基準
である。尚、本発明は下記の実施例、試験例などに拘束
されるものではなく、本発明の技術的思想の範囲内で任
意の変形をなし得ることは勿論である。Hereinafter, synthesis examples of the water-soluble copolymer of the present invention,
Production examples of AKD emulsion, various evaluation test examples of storage stability and mechanical stability of AKD emulsion, production examples of two-liquid mixing type surface sizing agent using water-soluble copolymer and AKD emulsion, and the two liquids Various evaluation test examples of the storage stability of the mixed surface sizing agent, the sizing property of the coated paper, the paper slipping property, etc. will be sequentially described. The following synthesis examples, production examples,
"%" And "parts" in Examples and Test Examples are basically based on weight. The present invention is not limited to the following examples and test examples, and it goes without saying that any modification can be made within the scope of the technical idea of the present invention.
【００４１】《水溶性共重合体の合成例》下記の合成例
１はスチレン／アクリル酸、合成例２はスチレン／アク
リル酸／マレイン酸、合成例３及び比較合成例１はスチ
レン／マレイン酸を単量体組成とする各共重合体の例で
ある。
(1)合成例１
攪拌機、冷却管及び温度計を具備した５００ｍＬの４つ
口フラスコに、トルエン４０ｇ、アクリル酸１５ｇ及び
スチレン３５ｇを仕込み、攪拌しながら加熱して還流温
度まで昇温した。一方、滴下ロートに、トルエン２０
ｇ、アクリル酸１５ｇ、スチレン３５ｇ、アゾイソブチ
ロニトリル１.５ｇ及びノルマルドデシルメルカプタン
１.２ｇを仕込み、均一に溶解した。次いで、この混合
溶液を１時間かけて前記反応容器に滴下し、さらに還流
温度で４時間熟成した。その後、これを冷却し、４８％
水酸化カリウム水溶液５３.６ｇを水１５０ｇに溶解し
て滴下し、反応生成物をケン化溶解した。次に、再度、
還流温度まで加熱してトルエンを留去し、冷却した後、
水で希釈して固形分２０％の水溶性共重合体の水溶液を
得た。この水溶性共重合体の酸価は２３０mgKOH／gであ
った(図１参照)。<< Synthesis Example of Water-Soluble Copolymer >> The following Synthesis Example 1 is styrene / acrylic acid, Synthesis Example 2 is styrene / acrylic acid / maleic acid, and Synthesis Example 3 and Comparative Synthesis Example 1 are styrene / maleic acid. It is an example of each copolymer having a monomer composition. (1) Synthesis Example 1 To a 500 mL four-necked flask equipped with a stirrer, a condenser and a thermometer, 40 g of toluene, 15 g of acrylic acid and 35 g of styrene were charged and heated with stirring to a reflux temperature. On the other hand, add toluene 20 to the dropping funnel.
g, 15 g of acrylic acid, 35 g of styrene, 1.5 g of azoisobutyronitrile and 1.2 g of normaldodecyl mercaptan were charged and uniformly dissolved. Next, this mixed solution was dropped into the reaction vessel over 1 hour, and further aged at reflux temperature for 4 hours. Then cool it to 48%
53.6 g of an aqueous potassium hydroxide solution was dissolved in 150 g of water and added dropwise to saponify and dissolve the reaction product. Then again
After heating to the reflux temperature to distill off the toluene and cool,
It was diluted with water to obtain an aqueous solution of a water-soluble copolymer having a solid content of 20%. The acid value of this water-soluble copolymer was 230 mgKOH / g (see FIG. 1).
【００４２】(2)合成例２
上記合成例１を基本としながら、図１の組成に従って、
単量体、水酸化カリウム水溶液の各量を変化させ、それ
以外の条件を上記合成例１と同様に操作して、固形分２
０％の水溶性共重合体のケン化物を得た。得られた水溶
性共重合体の酸価は２００mgKOH／gであった。(2) Synthesis Example 2 Based on the above Synthesis Example 1, according to the composition of FIG.
The amounts of the monomer and the potassium hydroxide aqueous solution were changed, and the other conditions were the same as in Synthesis Example 1 above to obtain a solid content of 2
A saponified product of 0% water-soluble copolymer was obtained. The acid value of the obtained water-soluble copolymer was 200 mgKOH / g.
【００４３】(3)合成例３
上記合成例１を基本としながら、図１の組成に従って、
単量体、水酸化カリウム水溶液量を変化させ、それ以外
の条件を上記合成例１と同様に操作して、固形分２５％
の水溶性共重合体のケン化物を得た。得られた水溶性共
重合体の酸価は３２０mgKOH／gであった。(3) Synthesis Example 3 Based on the above Synthesis Example 1, according to the composition of FIG.
The amount of the monomer and the aqueous potassium hydroxide solution was changed, and the other conditions were the same as in Synthesis Example 1 above to obtain a solid content of 25%.
A saponified product of the water-soluble copolymer of The acid value of the obtained water-soluble copolymer was 320 mgKOH / g.
【００４４】(4)比較合成例１
上記合成例１を基本としながら、図１の組成に従って、
単量体、水酸化カリウム水溶液量を変化させ、それ以外
の条件を上記合成例１と同様に操作して、固形分２５％
の水溶性共重合体のケン化物を得た。得られた水溶性共
重合体の酸価は４２０mgKOH／gであった。(4) Comparative Synthesis Example 1 Based on the above Synthesis Example 1, the composition of FIG.
The amount of the monomer and the aqueous potassium hydroxide solution was changed, and the other conditions were the same as in Synthesis Example 1 above to obtain a solid content of 25%.
A saponified product of the water-soluble copolymer of The acid value of the obtained water-soluble copolymer was 420 mgKOH / g.
【００４５】《ＡＫＤエマルションの製造例》
(1)製造例１
攪拌機、冷却管及び温度計を具備した５００ｍＬの４つ
口フラスコに、融点５０℃のＡＫＤ(オーペル；日本精
化社製)２００ｇを仕込み、８０℃まで昇温して溶融し
た。一方、攪拌機及び温度計を具備した１Ｌのフラスコ
に、窒素量が０.３５％である４級化カチオンデンプン
(ａ)を４３.２ｇ、水を６５０ｇ仕込み、９０℃まで昇
温し、４０分間温度保持して、カチオンデンプンを糊化
した水溶液を得た。溶融した前記ＡＫＤを７０℃まで冷
却した後、７０℃に温度保持した上記カチオンデンプン
の水溶液中に落とし込み、さらにナフタレンスルホン酸
塩―ホルマリン縮合物(デモールＴ；花王社製)を２.３
ｇ仕込み、ホモミキサーで粗乳化した後、同温度におい
て剪断力３００ＭＰａの条件でピストン式高圧乳化機に
２回通して、カチオンデンプンで乳化分散したＡＫＤエ
マルション(平均粒子径：０.６μm程度)を得た。次い
で、ＡＫＤエマルションに硫酸アルミニウム水溶液(Ａ
ｌ2Ｏ3として８％含有)を１０.４ｇ(金属換算で０.２２
％)加え、水で希釈し、固形分２０％、ゼータ電位＋１
１.２ｍＶのＡＫＤエマルションを得た。尚、上記ゼー
タ電位は、顕微鏡電気泳動法により、LAZER ZEE METER
MODEL 501(PEN KEM INC.製)の測定装置を用いて、下記
の手順〜で測定した。
ＡＫＤエマルションを水で５〜５０ｐｐｍ程度に希釈
し、印加電圧装置付きの平面セルに入れる。
セルに電圧をかけると、コロイド粒子自身が帯電する
電荷と反対側の電極に移動するので、印加電圧を変化さ
せて粒子が移動しなくなる電圧値を測定する。<< Production Example of AKD Emulsion >> (1) Production Example 1 In a 500 mL four-necked flask equipped with a stirrer, a cooling tube and a thermometer, 200 g of AKD (Opel; manufactured by Nippon Seika Co., Ltd.) having a melting point of 50 ° C. After charging, the temperature was raised to 80 ° C. to melt. On the other hand, in a 1 L flask equipped with a stirrer and a thermometer, a quaternized cationic starch with a nitrogen content of 0.35%
43.2 g of (a) and 650 g of water were charged, the temperature was raised to 90 ° C., and the temperature was kept for 40 minutes to obtain an aqueous solution of gelatinized cationic starch. After the molten AKD was cooled to 70 ° C., it was dropped into an aqueous solution of the above cationic starch kept at 70 ° C., and naphthalene sulfonate-formalin condensate (Demol T; manufactured by Kao Corporation) was added to 2.3.
After being g-prepared and roughly emulsified with a homomixer, the mixture was passed through a piston-type high-pressure emulsifier twice at the same temperature and a shearing force of 300 MPa to emulsify and disperse an AKD emulsion (average particle size: about 0.6 μm) with cationic starch. Obtained. Then, add aluminum sulfate aqueous solution (A
10.4 g (containing 8% as l 2 O 3 ) (0.22 in terms of metal)
%), Diluted with water, solid content 20%, zeta potential +1
A 1.2 mV AKD emulsion was obtained. In addition, the zeta potential was determined by LAZER ZEE METER
The measurement was carried out using the measuring device of MODEL 501 (manufactured by PEN KEM INC.) According to the following procedure. The AKD emulsion is diluted with water to about 5 to 50 ppm and placed in a flat cell with an applied voltage device. When a voltage is applied to the cell, the colloidal particles themselves move to the electrode on the side opposite to the charged charge, so the applied voltage is changed and the voltage value at which the particles do not move is measured.
【００４６】(2)製造例２
上記製造例１を基本としながら、図２の組成に従って、
硫酸アルミニウムの添加量を低減させ、それ以外の条件
を上記製造例１と同様に操作して、固形分２０％、ゼー
タ電位−２.７ｍＶのＡＫＤエマルションを得た。(2) Production Example 2 Based on the above Production Example 1, according to the composition of FIG.
The amount of aluminum sulfate added was reduced, and the other conditions were the same as in Production Example 1 above to obtain an AKD emulsion having a solid content of 20% and a zeta potential of -2.7 mV.
【００４７】(3)製造例３
上記製造例１を基本としながら、図２の組成に従って、
硫酸アルミニウムの添加量を増大させ、それ以外の条件
を上記製造例１と同様に操作して、固形分２０％、ゼー
タ電位＋１７.５ｍＶのＡＫＤエマルションを得た。(3) Production Example 3 Based on the above Production Example 1, according to the composition of FIG.
The amount of aluminum sulfate added was increased, and the other conditions were the same as in Production Example 1 above to obtain an AKD emulsion having a solid content of 20% and a zeta potential of +17.5 mV.
【００４８】(4)比較製造例１
上記製造例１を基本としながら、図２の組成に従って、
硫酸アルミニウムを添加せず、それ以外の条件を上記製
造例１と同様に操作して、固形分２０％、ゼータ電位−
４.８ｍＶのＡＫＤエマルションを得た。(4) Comparative Production Example 1 Based on the above Production Example 1, the composition of FIG.
Aluminum sulfate was not added, the other conditions were the same as in Production Example 1 above, solid content 20%, zeta potential-
A 4.8 mV AKD emulsion was obtained.
【００４９】(5)比較製造例２
上記製造例１を基本としながら、図２の組成に従って、
カチオンデンプンを品種(ａ)から、窒素量が０.５０％
である品種(ｂ)に代替し、硫酸アルミニウムを同量添加
し、それ以外の条件を上記製造例１と同様に操作して、
固形分２０％、ゼータ電位＋２２.５ｍＶのＡＫＤエマ
ルションを得た。(5) Comparative Production Example 2 Based on the above Production Example 1, the composition of FIG.
Nitrogen content is 0.50% from the variety (a) with cationic starch
In the same manner as in Production Example 1 above, except that aluminum sulfate was added in the same amount,
An AKD emulsion having a solid content of 20% and a zeta potential of +22.5 mV was obtained.
【００５０】(5)比較製造例３
上記製造例１を基本としながら、図２の組成に従って、
カチオンデンプンの品種(ａ)を品種(ｂ)に代替し、硫酸
アルミニウムを添加せず、それ以外の条件を上記製造例
１と同様に操作して、固形分２０％、ゼータ電位＋２
０.５ｍＶのＡＫＤエマルションを得た。(5) Comparative Production Example 3 Based on the above Production Example 1, the composition of FIG.
The cationic starch variety (a) was replaced with the variety (b), aluminum sulfate was not added, and the other conditions were the same as in Production Example 1 above, solid content 20%, zeta potential +2.
A 0.5 mV AKD emulsion was obtained.
【００５１】そこで、上記ＡＫＤエマルションを単独で
表面サイズ剤として使用した場合の各種評価試験を以下
に行った。
《ＡＫＤエマルションの評価試験例》
(1)貯蔵安定性試験
上記製造例１〜３及び比較製造例１〜３の各ＡＫＤエマ
ルション(固形分２０％)を200メッシュの金網(格子間：
７４μｍ)で濾過し、濾液を２０℃、１５日間保管し
た。その後、再び200メッシュの金網で濾過し、金網に
残った残渣を乾燥させた後、秤量し、固形分の残渣率
(％)を下式により算出して、残渣率の大小で貯蔵安定性
を評価した。
残渣率(％)＝｛残渣量(ｇ)／(濾過したサイズ剤(ｇ)×
0.20)｝×100Therefore, various evaluation tests were carried out below when the above AKD emulsion was used alone as a surface sizing agent. << Example of Evaluation Test of AKD Emulsion >> (1) Storage Stability Test Each AKD emulsion (solid content 20%) of the above Production Examples 1 to 3 and Comparative Production Examples 1 to 3 was wire mesh of 200 mesh (interstitial:
74 μm) and the filtrate was stored at 20 ° C. for 15 days. After that, it is filtered again through a 200-mesh wire net, the residue remaining on the wire net is dried, then weighed, and the solid residue ratio
(%) Was calculated by the following formula, and the storage stability was evaluated by the size of the residue rate. Residual ratio (%) = {residual amount (g) / (filtered sizing (g) ×
0.20)} × 100
【００５２】(2)機械安定性試験
JIS K 6392(マーロン試験)に基づいて、上記製造例１〜
３及び比較製造例１〜３の各ＡＫＤエマルション(固形
分２０％)を200メッシュの金網(格子間：７４μｍ)で濾
過し、濾液を金属カップに入れ、底面が平坦な金属棒を
装着し、下記の条件で金属棒に荷重を掛けながら回転さ
せることにより、剪断力を負荷した。
荷重：10kgf/cm2、回転数：1000±20rpm、剪断時間：10
分間
次いで、剪断後のサイズ剤を再び200メッシュの金網で
濾過し、金網に残った残渣を乾燥させた後、秤量して、
固形分の残渣率(％)を下式により算出した。
残渣率(％)＝｛残渣量(ｇ)／(濾過したサイズ剤(ｇ)×
0.20)｝×100(2) Mechanical stability test Based on JIS K 6392 (Marlon test), the above production examples 1 to
Each AKD emulsion (solid content 20%) of 3 and Comparative Production Examples 1 to 3 was filtered through a 200-mesh wire net (interstitial space: 74 μm), the filtrate was placed in a metal cup, and a metal rod having a flat bottom was attached, Shearing force was applied by rotating the metal rod under load under the following conditions. Load: 10 kgf / cm 2 , rotation speed: 1000 ± 20 rpm, shearing time: 10
After that, the sizing agent after shearing was again filtered through a 200-mesh wire mesh, the residue remaining on the wire mesh was dried, and then weighed.
The residual rate (%) of the solid content was calculated by the following formula. Residual ratio (%) = {residual amount (g) / (filtered sizing (g) ×
0.20)} × 100
【００５３】(3)酸化デンプンとの相溶性試験
上記製造例１〜３及び比較製造例１〜３の各ＡＫＤエマ
ルション0.1％と酸化デンプン5.0％を混合して塗工液を
調製し、この塗工液を200メッシュの金網(格子間：７４
μｍ)で濾過し、濾液を50℃で12時間保管した。その
後、再び200メッシュの金網で濾過し、金網に残った残
渣を乾燥させた後、秤量して、固形分の残渣率(％)を下
式により算出した。
残渣率(％)＝｛残渣量(ｇ)／(濾過した塗工液(ｇ)×0.0
51)｝×100(3) Compatibility Test with Oxidized Starch A coating solution was prepared by mixing 0.1% of each AKD emulsion of the above Production Examples 1 to 3 and Comparative Production Examples 1 to 5.0% of oxidized starch to prepare a coating solution. The working fluid is a 200 mesh wire mesh (interstitial space: 74
μm) and the filtrate was stored at 50 ° C. for 12 hours. Then, the mixture was filtered again with a 200-mesh wire net, the residue remaining on the wire net was dried, then weighed, and the residue rate (%) of the solid content was calculated by the following formula. Residual ratio (%) = {residual amount (g) / (filtered coating liquid (g) x 0.0
51)} × 100
【００５４】図３は上記ＡＫＤエマルションの各評価試
験の結果である。製造例１〜３では、各評価試験の残渣
率が小さく、貯蔵安定性、機械安定性、酸化デンプンと
の相溶性が共に良好であり、これらのＡＫＤエマルショ
ンを表面サイズ剤として単用した場合、予め調製済みの
エマルションを保存しても、また、塗工液を調製する際
に、酸化デンプンなどの他の塗工成分と撹拌・混合して
も品質が安定であり、表面サイズ剤としての適性を具備
することが判った。これに対して、比較製造例１〜３で
は、各評価試験の残渣率が大きく、貯蔵安定性、機械安
定性、酸化デンプンとの相溶性も劣っていた。以上のこ
とから、ＡＫＤエマルションのゼータ電位、並びに硫酸
アルミニウムの添加量は、表面サイズ剤としての適性を
具備させる点できわめて重要なことが判明した。ちなみ
に、製造例１のＡＫＤエマルションについて、後述する
２液混合型で示したサイズ性試験を行ったところ、酸性
紙のサイズ度は３８秒、中性紙では２０秒であった。FIG. 3 shows the results of each evaluation test of the AKD emulsion. In Production Examples 1 to 3, the residue rate in each evaluation test is small, storage stability, mechanical stability, and compatibility with oxidized starch are both good, and when these AKD emulsions are used alone as a surface sizing agent, The quality is stable even if the prepared emulsion is stored, or when it is mixed with other coating components such as oxidized starch when the coating liquid is prepared, and it is suitable as a surface sizing agent. It was found to have. On the other hand, in Comparative Production Examples 1 to 3, the residue rate in each evaluation test was high, and the storage stability, mechanical stability, and compatibility with oxidized starch were poor. From the above, it was found that the zeta potential of the AKD emulsion and the amount of aluminum sulfate added are extremely important in terms of suitability as a surface sizing agent. By the way, when the AKD emulsion of Production Example 1 was subjected to a sizing test shown in a two-liquid mixing type described later, the acid paper had a sizing degree of 38 seconds, and the neutral paper had a sizing degree of 20 seconds.
【００５５】次に、前記水溶性共重合体のケン化物と上
記ＡＫＤエマルションの２液を混合したタイプの表面サ
イズ剤について、先ず、その製造実施例を以下に述べ
る。
《２液混合型の表面サイズ剤の製造実施例》
(1)実施例１
２００ｍＬビーカーに前記合成例１で得られた水溶性共
重合体のケン化物６０ｇを採取した後、撹拌下のビーカ
ー中に上記製造例１のＡＫＤエマルション４０ｇを滴下
しながら添加して、固形分２０％の２液混合型表面サイ
ズ剤を得た。Next, the production examples of the surface sizing agent of the type in which the saponified product of the water-soluble copolymer and the two liquids of the AKD emulsion are mixed will be described below. << Production Example of Two-Liquid Mixing Type Surface Sizing Agent >> (1) Example 1 60 g of the saponified product of the water-soluble copolymer obtained in Synthesis Example 1 was collected in a 200 mL beaker, and then placed in a beaker under stirring. 40 g of the AKD emulsion of Production Example 1 was added dropwise to the above to obtain a two-liquid mixed surface sizing agent having a solid content of 20%.
【００５６】(2)実施例２〜１０
上記実施例１を基本としながら、図４に従って、合成例
１〜３の水溶性共重合体と製造例１〜３のＡＫＤエマル
ションの配合種類とその比率を変化させ、それ以外の条
件を実施例１と同様に操作し、水の添加によって、固形
分２０％に調整した２液混合型表面サイズ剤を得た。(2) Examples 2 to 10 Based on the above Example 1 and according to FIG. 4, according to FIG. 4, the compounding types and ratios of the water-soluble copolymers of Synthesis Examples 1 to 3 and the AKD emulsions of Production Examples 1 to 3 were used. Was changed and the other conditions were operated in the same manner as in Example 1 to obtain a two-liquid mixed surface sizing agent adjusted to a solid content of 20% by adding water.
【００５７】(3)比較例１〜５
上記実施例１を基本としながら、図４に従って、合成例
１と製造例１の組み合わせを、合成例３の水溶性共重合
体と比較製造例１〜３のＡＫＤエマルション、或は、比
較合成例１の水溶性共重合体と製造例１のＡＫＤエマル
ションの各組み合わせに変化させ、それ以外の条件を実
施例１と同様に操作し、水の添加によって、固形分２０
％に調整した比較例１〜４の２液混合型表面サイズ剤を
得た。ちなみに、比較例１は硫酸アルミニウムを含有し
ないＡＫＤエマルションを用いた例、比較例２は硫酸ア
ルミニウムを含有するが、ゼータ電位が＋２０ｍＶを越
えるＡＫＤエマルションを用いた例、比較例３は硫酸ア
ルミニウムを含有せず、ゼータ電位が＋２０ｍＶを越え
るＡＫＤエマルションを用いた例、比較例４は酸価が３
５０mgKOH／gを越える水溶性共重合体を用いた例であ
る。一方、比較例５は合成例１の水溶性共重合体のみを
使用し、ＡＫＤエマルションを使用しない例である。(3) Comparative Examples 1 to 5 Based on the above Example 1, the combination of Synthesis Example 1 and Production Example 1 was compared with the water-soluble copolymer of Synthesis Example 3 according to FIG. 3 or the combination of the water-soluble copolymer of Comparative Synthesis Example 1 and the AKD emulsion of Production Example 1 was changed, and the other conditions were the same as in Example 1, and water was added. , Solid content 20
%, The two-liquid mixed surface sizing agents of Comparative Examples 1 to 4 were obtained. By the way, Comparative Example 1 is an example using an AKD emulsion containing no aluminum sulfate, Comparative Example 2 contains aluminum sulfate, but an example using an AKD emulsion having a zeta potential exceeding +20 mV, Comparative Example 3 contains aluminum sulfate. No, and an example using an AKD emulsion in which the zeta potential exceeds +20 mV, Comparative Example 4 has an acid value of 3
This is an example using a water-soluble copolymer exceeding 50 mgKOH / g. On the other hand, Comparative Example 5 is an example in which only the water-soluble copolymer of Synthesis Example 1 is used and the AKD emulsion is not used.
【００５８】《２液混合型表面サイズの評価試験例》
(1)貯蔵安定性試験
実施例１〜１０及び比較例１〜５の各表面サイズ剤(固
形分20％)を200メッシュの金網(格子間：74μｍ)で濾過
した後、20℃、15日間保管して、保管中と保管後の状態
を目視観察し、下記の評価基準により貯蔵安定性を評価
した。尚、各表面サイズ剤の混合直後の粘度は10〜35mP
a・sであった。
〔評価基準〕
◎：粘度の上昇がなく安定に存在した。
○：11日経過後に粘度が増加傾向を示したが、100mPa・
s以下であり、使用に問題のないレベルであった。
×：11日経過後にクリーム状に固化し(粘度は1000mPa・
s前後)、使用が困難なレベルであった。<< Evaluation Test Example of Two-Liquid Mixing Type Surface Size >> (1) Storage Stability Test Each surface sizing agent of Examples 1 to 10 and Comparative Examples 1 to 5 (solid content 20%) was treated with a 200 mesh wire mesh ( After filtration through a lattice (74 μm), the mixture was stored at 20 ° C. for 15 days, the state during storage and the state after storage were visually observed, and the storage stability was evaluated according to the following evaluation criteria. The viscosity of each surface sizing agent immediately after mixing is 10 to 35 mP.
It was a ・ s. [Evaluation Criteria] A: Stable existence without increase in viscosity. ○: Viscosity tended to increase after 11 days, but 100mPa ・
It was below s, and was at a level where there was no problem in use. ×: Solidified into cream after 11 days (viscosity 1000 mPa
(around s), it was a level that was difficult to use.
【００５９】(2)サイズ性試験
上記実施例１〜１０及び比較例１〜５の各表面サイズ剤
0.1％と酸化デンプン5.0％を混合して塗工液を調製し、
下記の酸性原紙にサイズプレス塗工法に準拠した方法に
よって上記塗工液を塗布し、ドラム式ドライヤーを用い
て80℃、90秒の条件で乾燥して、酸性塗工紙を得た。
〔酸性原紙〕
坪量：72.4g／m2
硫酸バンドの添加量(対パルプ)：2％
紙面ｐＨ：5.2
また、上記酸性原紙を下記の中性原紙に代替し、同様の
方法で塗工液を塗布して、中性塗工紙を得た。
〔中性原紙〕
坪量：85.1g／m2
硫酸バンドの添加量(対パルプ)：0.7％
紙面ｐＨ：7.4
そして、温度23℃、相対湿度60％で30時間調湿した後、
ステキヒト法(JIS P 8122−1954)にて、酸性紙、中性紙
の各サイズ度(秒)を測定した。(2) Sizing test Each surface sizing agent of Examples 1 to 10 and Comparative Examples 1 to 5 above
Prepare a coating liquid by mixing 0.1% and oxidized starch 5.0%,
The above coating solution was applied to the acidic base paper described below by a method conforming to the size press coating method, and dried using a drum dryer at 80 ° C. for 90 seconds to obtain an acidic coated paper. [Acid base paper] Basis weight: 72.4 g / m 2 Addition amount of sulfuric acid band (relative to pulp): 2% Paper surface pH: 5.2 In addition, the above acid base paper is replaced with the following neutral base paper, and the same coating solution is used. Was applied to obtain a neutral coated paper. [Neutral base paper] Basis weight: 85.1 g / m 2 Addition amount of sulfuric acid band (vs. pulp): 0.7% Paper surface pH: 7.4 And after conditioning the temperature for 30 hours at a temperature of 23 ° C. and a relative humidity of 60%,
Each size degree (second) of acidic paper and neutral paper was measured by the Steckit method (JIS P 8122-1954).
【００６０】(3)紙滑り試験方法
上記サイズ性試験と同様の操作により塗工液を塗布した
酸性紙、中性紙を得た後、JIS P 8197−1987に基づいて
下記の手順で塗工紙の動摩擦係数を測定した。
水平板上に、塗工紙の塗工面が上向きになるように固
定する。
上記と同一の紙を、平坦な表面を持つ金属板(質量
が既知なもの)に塗工面が外面となるように固定する。
上記の金属板の一端に軽量ワイヤーを装着し、滑車
を介して金属板の他端を万能引っ張り試験機に装着す
る。
上記をの上に塗工面が合わさるように置き、引っ
張り試験機を10.0±0.2mm／分の速度で引っ張り、金属
板が動き出すピークの強度を静摩擦力とし、動いている
きの平均強度を動摩擦力として、下式により動摩擦係数
を測定する。
動摩擦係数＝動摩擦力(mN)／重りによる垂直加重(mN)(3) Paper slip test method Acidic paper and neutral paper coated with a coating solution were obtained by the same operation as in the above size test, and then coated according to the following procedure based on JIS P 8197-1987. The coefficient of dynamic friction of the paper was measured. Fix the coated paper on a horizontal plate with the coated surface facing upward. The same paper as the above is fixed to a metal plate (having a known mass) having a flat surface such that the coated surface is the outer surface. A lightweight wire is attached to one end of the above metal plate, and the other end of the metal plate is attached to a universal tensile tester via a pulley. Place the coated surface on top of the above, pull the tensile tester at a speed of 10.0 ± 0.2 mm / min, and set the peak strength at which the metal plate starts to move as the static friction force, and the average strength of the moving wheel as the dynamic friction force. As, the dynamic friction coefficient is measured by the following formula. Dynamic friction coefficient = Dynamic friction force (mN) / Vertical load by weight (mN)
【００６１】(4)酸化デンプンとの相溶性試験
ＡＫＤエマルションを単用した場合の前記酸化デンプン
との相溶性試験を基本として、前記試験でのＡＫＤエマ
ルション0.1％に替えて、実施例１〜１０及び比較例１
〜５の各表面サイズ剤0.1％を使用し、それ以外の条件
を前記試験と同様に設定して、本相溶性試験を行った。(4) Compatibility Test with Oxidized Starch Based on the compatibility test with the above-mentioned oxidized starch when the AKD emulsion was used alone, the AKD emulsion in the above test was replaced with 0.1%, and Examples 1 to 10 were used. And Comparative Example 1
The main compatibility test was carried out by using each surface sizing agent of 0.1 to 5% and setting the other conditions in the same manner as the above test.
【００６２】図５は２液混合型の表面サイズ剤、或は、
当該サイズ剤を用いた塗工紙の各種評価試験の結果であ
る。先ず、実施例１〜１０の表面サイズ剤は、前記図４
に示すように、通常ではＡＫＤが不安定になるアルカリ
側のｐＨ条件になっているが、この条件にも拘わらず、
比較例１〜４とは異なり、優れた貯蔵安定性が認められ
た。酸化デンプンとの相溶性も同様であった。実施例１
〜１０の表面サイズ剤を塗工した紙では、酸性紙〜中性
紙で優れたサイズ性を示し、特に、中性サイズ性に劣る
水溶性共重合体のみを使用した比較例５に比べると、そ
の中性サイズ性の改善は明らかである。また、実施例１
〜１０の塗工紙の動摩擦係数は、比較例５と同様か遜色
のない水準を示し、前記製造例１のＡＫＤエマルション
単独について紙滑り試験を行ったところ、動摩擦係数は
０.３７であったことから、ＡＫＤを用いた場合に特有
の摩擦係数の低下も余りないことが明らかとなった。FIG. 5 shows a two-liquid mixed surface sizing agent, or
It is a result of various evaluation tests of the coated paper using the sizing agent. First, the surface sizing agents of Examples 1 to 10 are the same as those shown in FIG.
As shown in, normally, the pH condition is on the alkaline side where AKD becomes unstable, but in spite of this condition,
Different from Comparative Examples 1 to 4, excellent storage stability was observed. The compatibility with oxidized starch was similar. Example 1
In the paper coated with the surface sizing agent of No. 10 to 10, excellent sizing property is shown in acidic paper to neutral paper, and in particular, compared with Comparative Example 5 using only a water-soluble copolymer having poor neutral sizing property. , Its neutral sizing improvement is clear. In addition, Example 1
The coated papers of Nos. 10 to 10 showed the same level of dynamic friction as that of Comparative Example 5 or a level comparable to that of Comparative Example 5, and when the AKD emulsion alone of Production Example 1 was subjected to a paper slip test, the dynamic friction coefficient was 0.37. Therefore, it became clear that the friction coefficient peculiar to AKD was not significantly decreased.
【００６３】この点をさらに詳述すると、実施例１〜４
は同種類の水溶性共重合体とＡＫＤエマルションを使用
し、その配合比を変化させたものであるが、ＡＫＤエマ
ルションの配合比が少なめの実施例３〜４は、実施例１
〜２より貯蔵安定性が向上していた。実施例３、実施例
５〜６は両者の配合比とＡＫＤエマルションの種類が同
じで、水溶性共重合体の種類を変化させたものである
が、水溶性共重合体の酸価が３００以下の実施例３と５
は、実施例６より貯蔵安定性が改善された。実施例５、
実施例８〜９は両者の配合比と水溶性共重合体の種類が
同じで、ＡＫＤエマルションの種類を変化させたもので
あるが、ＡＫＤエマルションのゼータ電位が低く、硫酸
アルミニウムの含有量が少ない実施例５と８は、実施例
９より貯蔵安定性が改善された。また、ＡＫＤエマルシ
ョンの配合比が最小である実施例４においても、中性紙
のサイズ性は比較例５に比べて高水準であり、逆に、Ａ
ＫＤエマルションの配合比が最大である実施例１０の摩
擦係数は比較例５に比べてそれほどの低下が見られず、
共に表面サイズ剤としての適性を良好に保持していた。This point will be described in more detail. Examples 1 to 4
Is a water-soluble copolymer of the same kind and an AKD emulsion are used, and the compounding ratio thereof is changed, but Examples 3 to 4 in which the compounding ratio of the AKD emulsion is small are those of Example 1
Storage stability was improved from ~ 2. In Example 3 and Examples 5 to 6, the compounding ratio of the both and the type of the AKD emulsion were the same, and the type of the water-soluble copolymer was changed, but the acid value of the water-soluble copolymer was 300 or less. Examples 3 and 5
Had improved storage stability as compared to Example 6. Example 5,
Examples 8 to 9 have the same blending ratio and the same kind of the water-soluble copolymer, and the kinds of the AKD emulsion are changed, but the zeta potential of the AKD emulsion is low and the content of aluminum sulfate is small. Examples 5 and 8 have improved storage stability over Example 9. Also in Example 4 in which the compounding ratio of the AKD emulsion was the smallest, the size property of the neutral paper was higher than that in Comparative Example 5, and conversely, A
The friction coefficient of Example 10 in which the compounding ratio of the KD emulsion is the maximum is not so much lower than that of Comparative Example 5,
Both of them maintained good suitability as a surface sizing agent.
【００６４】以上のように、特定のゼータ電位を有し、
水溶性金属塩を含有する特殊なＡＫＤエマルションに、
特定の酸価を有する水溶性共重合体を併用した実施例１
〜１０の表面サイズ剤は、両者の相溶性が良好で貯蔵安
定性に優れ、塗工直前に２液を併用しても勿論良いが、
予め２液を混合保存しても性能低下がないことが明らか
になった。また、酸化デンプンなどの他の塗工成分との
相溶性も良かった。しかも、これら実施例１〜１０の表
面サイズ剤を塗工した紙では、水溶性共重合体による中
性サイズ性の不足分をＡＫＤエマルションの併用で補強
するとともに、ＡＫＤによる摩擦係数の低下を水溶性共
重合体で防止することができ、従来の２液混合型表面サ
イズ剤にはない優れた適性を兼備することが確認でき
た。尚、上記各試験中には記載しなかったが、ＡＫＤエ
マルションを単用した場合の前記機械安定性試験を、本
実施例の２液混合型表面サイズ剤に適用したところ、実
施例１〜１０ともに良好な機械安定性を示し、使用直前
に２液を撹拌混合しても粕はほとんど発生しないことが
認められた。このことは、２液混合型表面サイズの優れ
た貯蔵安定性からも推測できるが、当該確認試験により
この点が実証的に裏付けられた。As described above, having a specific zeta potential,
Special AKD emulsion containing water-soluble metal salt,
Example 1 in which a water-soluble copolymer having a specific acid value is used in combination
Surface sizing agents Nos. 10 to 10 have good compatibility with each other and are excellent in storage stability. Of course, two liquids may be used in combination immediately before coating,
It was clarified that the performance did not deteriorate even if the two solutions were mixed and stored in advance. The compatibility with other coating components such as oxidized starch was also good. Moreover, in the papers coated with the surface sizing agents of Examples 1 to 10, the insufficient neutral sizing property due to the water-soluble copolymer is reinforced by the combined use of the AKD emulsion, and the decrease in the friction coefficient due to AKD is reduced by the water-soluble copolymer. It has been confirmed that it can be prevented by a sex copolymer and that it also has excellent suitability that conventional two-liquid mixed surface sizing agents do not have. Although not described in each of the above tests, the mechanical stability test when an AKD emulsion was used alone was applied to the two-liquid mixed surface sizing agent of this Example, and Examples 1 to 10 were obtained. Both showed good mechanical stability, and it was confirmed that even if the two liquids were mixed by stirring immediately before use, almost no lees were generated. This can be inferred from the excellent storage stability of the two-liquid mixed type surface size, but this confirmation test empirically confirmed this point.
【図１】水溶性共重合体の単量体組成、ｐＨ、粘度、酸
価などを示す図表である。FIG. 1 is a chart showing the monomer composition, pH, viscosity, acid value, etc. of a water-soluble copolymer.
【図２】ＡＫＤエマルションの硫酸アルミニウム含有
量、粘度、ゼータ電位などを示す図表である。FIG. 2 is a table showing aluminum sulfate content, viscosity, zeta potential, etc. of AKD emulsion.
【図３】ＡＫＤエマルションを単用した表面サイズ剤の
貯蔵安定性、機械安定性、酸化デンプンとの相溶性の各
試験結果を示す図表である。FIG. 3 is a table showing the test results of storage stability, mechanical stability, and compatibility with oxidized starch of a surface sizing agent using an AKD emulsion alone.
【図４】２液混合型の表面サイズ剤における水溶性共重
合体とＡＫＤエマルションの種類とその配合比率、ｐ
Ｈ、粘度を示す図表である。FIG. 4 shows the types of water-soluble copolymer and AKD emulsion in a two-liquid mixed surface sizing agent and their mixing ratios, p.
3 is a chart showing H and viscosity.
【図５】２液混合型の表面サイズ剤の貯蔵安定性、サイ
ズ性、紙滑り性、酸化デンプンとの相溶性の各試験結果
を示す図表である。FIG. 5 is a table showing test results of storage stability, sizing property, paper slipping property, and compatibility with oxidized starch of a two-liquid mixed surface sizing agent.
Claims (10)
オン基含有高分子化合物で水中に乳化分散し、水溶性金
属塩を含有して、ゼータ電位を−５〜＋２０ｍＶに調整
したＡＫＤエマルションからなることを特徴とする水溶
性高分子化合物との併用適性を備えたＡＫＤ系表面サイ
ズ剤。1. An AKD emulsion in which an alkyl ketene dimer (AKD) is emulsified and dispersed in a cationic group-containing polymer compound in water, contains a water-soluble metal salt, and has a zeta potential adjusted to -5 to +20 mV. An AKD-based surface sizing agent having suitability for use in combination with a characteristic water-soluble polymer compound.
性又は両性の水溶性高分子化合物であり、 ＡＫＤに対して、カチオン基含有高分子化合物を１０〜
２５重量％含有することを特徴とする請求項１に記載の
水溶性高分子化合物との併用適性を備えたＡＫＤ系表面
サイズ剤。2. The cationic group-containing polymer compound is a cationic or amphoteric water-soluble polymer compound, and the cationic group-containing polymer compound is added to AKD in an amount of 10 to 10.
25% by weight of the AKD surface sizing agent, which is suitable for combination with the water-soluble polymer compound according to claim 1.
算で０.００５〜２重量％含有することを特徴とする請
求項１又は２に記載の水溶性高分子化合物との併用適性
を備えたＡＫＤ系表面サイズ剤。3. The suitability for combination with the water-soluble polymer compound according to claim 1 or 2, wherein the water-soluble metal salt is contained in 0.005 to 2% by weight in terms of metal based on AKD. An equipped AKD surface sizing agent.
ニオン性単量体を反応させた酸価１５０〜３５０mgKOH
／gの水溶性共重合体と、 (Ｂ)請求項１〜３のいずれか１項のＡＫＤエマルション
とを含有する表面サイズ剤。4. An acid value of 150 to 350 mg KOH obtained by reacting (A) a hydrophobic monomer with a carboxylic acid group-containing anionic monomer.
A surface sizing agent containing / g of a water-soluble copolymer and (B) the AKD emulsion according to any one of claims 1 to 3.
ン(Ｂ)の混合割合が、Ａ／Ｂ＝５０〜９９重量部／５０
〜１重量部である請求項４に記載の表面サイズ剤。5. The mixing ratio of the water-soluble copolymer (A) and the AKD emulsion (B) is A / B = 50 to 99 parts by weight / 50.
The surface sizing agent according to claim 4, which is ˜1 part by weight.
リル酸エステル類などであり、 カルボン酸基含有アニオン性単量体がアクリル酸、メタ
クリル酸、マレイン酸、イタコン酸などである請求項４
又は５に記載の表面サイズ剤。6. The hydrophobic monomer is styrene, (meth) acrylic acid ester, etc., and the carboxylic acid group-containing anionic monomer is acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc. Item 4
Or the surface sizing agent according to item 5.
リル酸、スチレンとアクリル酸とマレイン酸、又はスチ
レンとマレイン酸を単量体組成とする共重合体であるこ
とを特徴とする請求項４〜６のいずれか１項に記載の表
面サイズ剤。7. The water-soluble copolymer (A) is a copolymer having a monomer composition of styrene and acrylic acid, styrene and acrylic acid and maleic acid, or styrene and maleic acid. The surface sizing agent according to any one of claims 4 to 6.
面サイズ剤を塗工した紙。8. A paper coated with the surface sizing agent according to claim 1.
コールなどの表面強度用水溶性高分子化合物を表面サイ
ズ剤と共に塗工した請求項８に記載の紙。9. The paper according to claim 8, which is further coated with a water-soluble polymer compound for surface strength such as oxidized starch and polyvinyl alcohol together with a surface sizing agent.
の存在下で湿式抄造した紙であることを特徴とする請求
項８又は９の紙。10. The paper according to claim 8 or 9, characterized in that the paper is wet papermaking in the presence of a sulfuric acid band and calcium carbonate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008031579A (en) * | 2006-07-27 | 2008-02-14 | Sakata Corp | Printed matter of corrugated paper and method for producing the same |
| JP2008248399A (en) * | 2007-03-29 | 2008-10-16 | Nippon Paper Industries Co Ltd | Newsprint paper for offset printing |
| JP2008308787A (en) * | 2007-06-14 | 2008-12-25 | Arakawa Chem Ind Co Ltd | Surface-sizing liquid for papermaking, and printing paper |
| JP2010513734A (en) * | 2006-12-20 | 2010-04-30 | ビーエーエスエフ ソシエタス・ヨーロピア | Paper sizing mixture |
| JP2010255161A (en) * | 2009-03-31 | 2010-11-11 | Arakawa Chem Ind Co Ltd | Surface-coating liquid for papermaking and paper |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008031579A (en) * | 2006-07-27 | 2008-02-14 | Sakata Corp | Printed matter of corrugated paper and method for producing the same |
| JP2010513734A (en) * | 2006-12-20 | 2010-04-30 | ビーエーエスエフ ソシエタス・ヨーロピア | Paper sizing mixture |
| JP2008248399A (en) * | 2007-03-29 | 2008-10-16 | Nippon Paper Industries Co Ltd | Newsprint paper for offset printing |
| JP2008308787A (en) * | 2007-06-14 | 2008-12-25 | Arakawa Chem Ind Co Ltd | Surface-sizing liquid for papermaking, and printing paper |
| JP2010255161A (en) * | 2009-03-31 | 2010-11-11 | Arakawa Chem Ind Co Ltd | Surface-coating liquid for papermaking and paper |
| JP2011203672A (en) * | 2010-03-26 | 2011-10-13 | Fuji Xerox Co Ltd | Electrophotographic paper |
| JP2012007283A (en) * | 2010-05-27 | 2012-01-12 | Arakawa Chem Ind Co Ltd | Papermaking surface sizing agent, surface sizing coating liquid and paper |
| JP2012139992A (en) * | 2010-12-15 | 2012-07-26 | Oji Paper Co Ltd | Inkjet paper |
| WO2012152997A1 (en) * | 2011-05-06 | 2012-11-15 | Upm-Kymmene Corporation | Hydrophobic coating and a method for producing hydrophobic surface |
| JP2013049935A (en) * | 2011-08-31 | 2013-03-14 | Daio Paper Corp | Coated paper |
| CN102505569A (en) * | 2011-12-07 | 2012-06-20 | 山东华泰纸业股份有限公司 | Process for applying neutral sizing agent to surface coating |
| CN113089362A (en) * | 2021-04-08 | 2021-07-09 | 山东仁丰特种材料股份有限公司 | Method for producing wine label base paper by fourdrinier vat paper machine |
| CN116289311A (en) * | 2023-03-29 | 2023-06-23 | 浙江百斯特化工有限公司 | Preparation method of high-stability AKD sizing agent |
| CN116289311B (en) * | 2023-03-29 | 2023-09-29 | 浙江百斯特化工有限公司 | Preparation method of high-stability AKD sizing agent |
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