JP2006070268A - Fluidity modifier, paper coating liquid containing fluidity modifier and coated paper - Google Patents
Fluidity modifier, paper coating liquid containing fluidity modifier and coated paper Download PDFInfo
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Abstract
Description
本発明は、新規かつ改良された流動性改質剤、及びこれを含む紙塗工液、並びにこれを塗工した塗工紙に関し、特に詳しくは、Ｂ型粘度が低く、ハイシェア（ＨＳ）粘度が高く、さらにすぐれた流動性付与特性を有し、しかも良好な保水性付与特性を有する流動性改質剤、及びこれを含む紙塗工液、並びにこれを塗工した塗工紙に関する。 The present invention relates to a novel and improved fluidity modifier, a paper coating solution containing the same, and a coated paper coated with the same, and more particularly, has a low B-type viscosity and a high shear (HS) viscosity. More particularly, the present invention relates to a fluidity modifier having a high fluidity-imparting property and excellent water retention property, a paper coating solution containing the fluidity-modifying agent, and a coated paper coated with the fluidity modifier.
一般に、印刷用紙には、平滑性、光沢性、印刷適性等を改善する目的から、その表面に所定の紙塗工液が塗工される。この紙塗工液は、通常、クレー、重質炭酸カルシウム等の白色顔料と、ラテックス、澱粉等のバインダーとを水に分散させたスラリーとして調整され、これを適当な濃度に希釈し用いられる。実際の操業においては、該紙塗工液は、調整タンクから紙塗工機に供給された後、高速走行中の紙基材の表面上に連続的に塗工されるが、塗布された紙塗工液のうち、余剰分はブレード等の塗工ヘッドで除去される。
従って、紙基材上には薄膜状の塗工液からなる層が形成されるため、その後に乾燥することによって所望とする薄膜の塗工層が紙基材の表面上に形成された塗工紙を得ることができる。
また、紙基材から除去された余剰の塗工液は調整タンクに戻され、新たな紙塗工液と混合されて再使用に供されるのが一般的である。
In general, a predetermined paper coating solution is applied to the surface of a printing paper for the purpose of improving smoothness, gloss, printability and the like. This paper coating solution is usually prepared as a slurry in which a white pigment such as clay or heavy calcium carbonate and a binder such as latex or starch are dispersed in water, and this is diluted to an appropriate concentration and used. In actual operation, the paper coating solution is supplied continuously from the adjustment tank to the paper coating machine and then continuously applied onto the surface of the paper substrate that is running at high speed. Of the coating liquid, the excess is removed by a coating head such as a blade.
Therefore, a layer made of a thin film-like coating solution is formed on the paper base material. Therefore, a coating film in which a desired thin film coating layer is formed on the surface of the paper base material by drying thereafter. Paper can be obtained.
Moreover, it is general that the excess coating liquid removed from the paper substrate is returned to the adjustment tank, mixed with a new paper coating liquid, and reused.
近年、塗工紙の生産性向上の目的から、塗工の高速化が要求され、その１つとして紙基材の表面上への塗工液の高速塗工化が望まれている。
また、用途によって種々の顔料が使用され、使用される顔料によっては塗工操業性が大きく変化してくる。特に焼成クレイやプラスチックピグメント等、極端に流動性が乏しい顔料を使用する紙塗工液はそのレオロジーの影響で塗工が困難となり、また、ロールコーター等の塗工方式が異なると要求される流動性も変わり、適切なレオロジーが紙塗工液に求められてくる。このような塗工方式では通常のブレードコーター塗工とは反対に低せん断速度下においては粘度が低く、高せん断速度下では適度な粘度を有することが求められることがある。そのような場合にはＯ／Ｗ型の流動性改質剤では目的が達成できない。
同様に焼成クレイやプラスチックピグメント等の流動性の悪い顔料ではやはり塗工性能が落ち、通常のＯ／Ｗ型の流動性改質剤においては塗工性能を向上させることはできない。
In recent years, high-speed coating has been demanded for the purpose of improving the productivity of coated paper, and as one of them, high-speed coating of a coating liquid on the surface of a paper substrate is desired.
Various pigments are used depending on the application, and coating operability varies greatly depending on the pigment used. In particular, paper coating solutions that use pigments with extremely poor fluidity, such as calcined clay and plastic pigments, are difficult to apply due to the effect of their rheology, and the flow required when the coating method of roll coaters is different. The nature changes, and appropriate rheology is required for paper coating solutions. In such a coating system, it is sometimes required that the viscosity is low at a low shear rate and an appropriate viscosity is obtained at a high shear rate, as opposed to normal blade coater coating. In such a case, the object cannot be achieved with an O / W type fluidity modifier.
Similarly, with poorly flowable pigments such as calcined clay and plastic pigment, the coating performance is also lowered, and with ordinary O / W type fluidity modifiers, the coating performance cannot be improved.
更に紙塗工液は、充分な保水性を有するものであることが要求される。保水性が不充分である場合には、塗工液中の水分が紙基材へと急激に浸透、移行し易くなるため、紙基材上に形成された薄膜状の塗工液からなる層のうちの紙基材と接触する部分において濃度上昇が引き起こされる場合があり、得られる塗工紙に品質上の欠陥を生じたり、操業上の不具合を生じたりするという問題がある。 Furthermore, the paper coating solution is required to have sufficient water retention. When the water retention is insufficient, the water in the coating solution is likely to rapidly penetrate and migrate to the paper substrate, so a layer made of a thin film coating solution formed on the paper substrate. Of these, there is a case where a density increase is caused in a portion in contact with the paper base material, and there is a problem that a defect in quality occurs in the obtained coated paper or a problem in operation occurs.
上記の問題を解決するため、従来の紙塗工液は、適度な保水力を保ちながらＨＳ粘度を低く抑えることで対応してきた。しかし、ロールコーター等では塗工量が着きにくくなり、塗料の付着量が上がらないという問題を有する。さらに焼成クレイやプラスチックピグメント等の配合塗料では極端に保水力が低く、かつ、流動性が悪いため低濃度での塗工が行われている。そのため、同様に塗料の付着量が上がらず、塗工紙の品質や塗工操業性に問題を生じる。
具体的には、例えば、顔料、接着剤及びアクリルアミド類−不飽和カルボン酸共重合体からなる組成物を含有する紙塗工液（特許文献１参照）、（ａ）エチレン性不飽和カルボン酸（塩）、（ｂ）（メタ）アクリロニトリル及び（ｃ）その他の共重合可能な単量体の共重合体からなる紙塗被塗料用バインダー（特許文献２参照）等が提案されている。
In order to solve the above problems, the conventional paper coating liquid has been coped with by keeping the HS viscosity low while maintaining an appropriate water retention capacity. However, a roll coater or the like has a problem that the amount of coating is difficult to reach and the amount of paint applied does not increase. Furthermore, blended paints such as baked clay and plastic pigments are extremely low in water retention and poor in fluidity, and thus are applied at low concentrations. For this reason, the amount of the applied paint does not increase, which causes a problem in the quality of coated paper and coating operability.
Specifically, for example, a paper coating solution containing a composition comprising a pigment, an adhesive, and an acrylamide-unsaturated carboxylic acid copolymer (see Patent Document 1), (a) an ethylenically unsaturated carboxylic acid ( Salts), (b) (meth) acrylonitrile, and (c) binders for paper coating materials comprising copolymers of other copolymerizable monomers have been proposed (see Patent Document 2).
しかしながら、特許文献１の紙塗工組成物では、Ｂ型粘度が高い上、ハイシェア粘度は低く、保水性を持たせることは困難であり、特にハイシェア粘度アップには限界がある。そのためロールコーター等では粘性の低い塗工カラーに対しては着量アップも困難である。 However, the paper coating composition of Patent Document 1 has a high B-type viscosity, a low high shear viscosity, and it is difficult to impart water retention, and there is a limit to increasing the high shear viscosity. For this reason, it is difficult for a roll coater or the like to increase the amount of coating for a coating color having a low viscosity.
また、特許文献２の紙塗被塗料用バインダーを紙塗工液に用いた場合には、特許文献１と同じような問題があり、また本文献はバインダーに関するものであり、本発明のようにハイシェア粘度を上げるものではなく、本発明と本質的に異なるものである。 Moreover, when the binder for paper coating paints of patent document 2 is used for a paper coating liquid, there exists a problem similar to patent document 1, and this document is related to a binder, and is like this invention. It does not increase the high shear viscosity and is essentially different from the present invention.
本発明は、Ｂ型粘度が低く、ハイシェア粘度が高く、良好な流動性を付与することができ、しかも保水性付与特性にも優れた流動性改質剤、及びこの流動性改質剤を含む塗工の高速化が可能な紙塗工液を提供することを目的とする。
また本発明は、この紙塗工液を適用した嵩高で平滑性の高い、良好な品質を有する塗工紙を提供することを目的とする。
The present invention includes a fluidity modifier having a low B-type viscosity, a high high shear viscosity, good fluidity, and excellent water retention properties, and the fluidity modifier. An object of the present invention is to provide a paper coating solution capable of high-speed coating.
Another object of the present invention is to provide a coated paper having a good quality with a high bulkiness and smoothness to which the paper coating solution is applied.
本発明者は、上記のような効果を有する流動性改質剤、特に紙塗工液について鋭意検討した結果、これには上記したような特定のアクリル系共重合体のＷ／Ｏ型エマルジョンが有用であることを見い出し、本発明を完成するに至ったものである。 As a result of intensive studies on the fluidity modifier having the above-described effects, particularly a paper coating solution, the present inventors have found that a specific acrylic copolymer W / O emulsion as described above is included. It has been found useful, and has led to the completion of the present invention.
即ち、本発明の上記課題は、下記［１］〜［４］により達成される。
［１］下記式（１）で示され重量平均分子量が４．０×１０６〜５．０×１０７であるアクリル系共重合体のＷ／Ｏ型エマルジョンからなることを特徴とする流動性改質剤。
That is, the said subject of this invention is achieved by following [1]-[4].
[1] Fluidity characterized by comprising a W / O emulsion of an acrylic copolymer represented by the following formula (1) and having a weight average molecular weight of 4.0 × 10 6 to 5.0 × 10 7 Modifier.
［２］前記アクリル系共重合体が、前記式（１）におけるｍとｎの比率が９５：５〜５０：５０の共重合体であることを特徴とする前記第［１］項に記載の流動性改質剤。
［３］少なくとも顔料及びバインダーを含む混合原料に対して、流動性改質剤を添加してなる紙塗工液であって、該流動性改質剤が、前記［１］項又は第［２］項に記載の流動性改質剤であることを特徴とする紙塗工液。
［４］紙基材に、前記第［３］項に記載の紙塗工液を塗工したことを特徴とする塗工紙。
[2] The item [1], wherein the acrylic copolymer is a copolymer having a ratio of m to n in the formula (1) of 95: 5 to 50:50. Fluidity modifier.
[3] A paper coating liquid obtained by adding a fluidity modifier to a mixed raw material containing at least a pigment and a binder, wherein the fluidity modifier is the item [1] or [2] ] The paper coating liquid characterized by being the fluidity modifier described in the item.
[4] A coated paper, wherein the paper base material is coated with the paper coating solution described in [3] above.
本発明の流動性改質剤は、低いＢ型粘度、高いハイシェア粘度、さらにすぐれた流動性付与特性を有し、しかも優れた保水性を付与することができる。
また、本発明の紙塗工液は、上記流動性改質剤を含有することにより、Ｂ型粘度が低く、ハイシェア粘度が高く、かつ、流動性および保水性に優れたものである。
そして、本発明の紙塗工液を用いることによって、塗工の高速化が達成でき、塗工紙の生産性が向上すると共に、得られた塗工紙は嵩高で平滑性に優れた高品質のものである。
The fluidity modifier of the present invention has a low B-type viscosity, a high high shear viscosity, and excellent fluidity-imparting properties, and can impart excellent water retention.
In addition, the paper coating solution of the present invention contains the above fluidity modifier, and thus has a low B-type viscosity, a high high shear viscosity, and excellent fluidity and water retention.
And by using the paper coating liquid of the present invention, high-speed coating can be achieved, the productivity of the coated paper is improved, and the obtained coated paper is bulky and has high quality with excellent smoothness. belongs to.
（流動性改質剤）
本発明の流動性改質剤は、下記式（１）で示されるアクリル系共重合体のＷ／Ｏ型エマルジョンからなるものである。
(Flowability modifier)
The fluidity modifier of the present invention comprises a W / O emulsion of an acrylic copolymer represented by the following formula (1).
上記アクリル系共重合体の構造は、ランダム、ブロック等いずれでもよい。
The structure of the acrylic copolymer may be random or block.
上記アクリル系共重合体のｍとｎの比率は、９５：５〜５０：５０が好ましい。これは、ｍ、ｎが上記範囲外では、目的とするＷ／Ｏ型エマルジョンが得られ難く、Ｂ型粘度、ハイシェア粘度、流動性、保水性も、目的とするものに達成することが容易でない。
また、該アクリル系共重合体の重量平均分子量は、４．０×１０６〜５．０×１０７の範囲のものである。これは、重量平均分子量が４．０×１０６より低いと、ハイシェア粘度が低くなるという問題があり、逆に５．０×１０７より高いとＢ型粘度が高くなるという不利がみられる。
該アクリル系共重合体の好ましい重量平均分子量は、８．０×１０６〜３．０×１０７である。
The ratio of m and n in the acrylic copolymer is preferably 95: 5 to 50:50. If m and n are outside the above ranges, the desired W / O emulsion is difficult to obtain, and the B-type viscosity, high shear viscosity, fluidity and water retention are not easily achieved. .
The weight average molecular weight of the acrylic copolymer is in the range of 4.0 × 10 6 to 5.0 × 10 7 . When the weight average molecular weight is lower than 4.0 × 10 6 , there is a problem that the high shear viscosity is lowered. On the contrary, when the weight average molecular weight is higher than 5.0 × 10 7 , there is a disadvantage that the B-type viscosity is increased.
A preferable weight average molecular weight of the acrylic copolymer is 8.0 × 10 6 to 3.0 × 10 7 .
本発明の流動性改質剤における重要な特徴の１つはアクリル系共重合体をＷ／Ｏ型エマルジョンの形とすることである。
このＷ／Ｏ型エマルジョンの製造は、例えば有機溶剤に、活性剤を室温にて添加し均一混合した後、これに水に溶解させたアクリル酸ナトリウムとアクリルアミドとを加えプレエマルジョンを合成し、次にこのプレエマルジョンの一部に重合開始剤の一部を加え温度５０〜５５℃に維持し、数分間ないし数１０分間攪拌する。ついでこのプレエマルジョンを攪拌下、温度６０℃未満に維持しつつ残りのプレエマルジョンと残りの重合開始剤を少量ずつ連続的に添加し、その後８０℃付近まで加熱し、その状態で約３０分間熟成することにより合成することができる。固形分としては２０〜６０質量％である。
本発明では、Ｗ／Ｏ型エマルジョンとすることが重要であり、これがＯ／Ｗ型の場合には、前記したような効果を得ることができない。
One important feature of the flow modifier of the present invention is that the acrylic copolymer is in the form of a W / O emulsion.
This W / O type emulsion is produced, for example, by adding an active agent to an organic solvent at room temperature and mixing it uniformly, and then adding sodium acrylate and acrylamide dissolved in water to synthesize a pre-emulsion. In addition, a part of the polymerization initiator is added to a part of this pre-emulsion, and the temperature is maintained at 50 to 55 ° C., followed by stirring for several minutes to several tens of minutes. Next, the remaining pre-emulsion and the remaining polymerization initiator are continuously added little by little while the pre-emulsion is maintained at a temperature of less than 60 ° C. with stirring, and then heated to about 80 ° C. and aged for about 30 minutes in that state. Can be synthesized. The solid content is 20 to 60% by mass.
In the present invention, it is important to use a W / O type emulsion. If this is an O / W type, the above-described effects cannot be obtained.
本発明において使用する有機溶剤としては、具体的にはトルエン、キシレン、鉱物油、ケロシン、イソパラフィン等を挙げることができる。 Specific examples of the organic solvent used in the present invention include toluene, xylene, mineral oil, kerosene, and isoparaffin.
また、活性剤としては、具体的にはソルビタンモノステアレート、ソルビタンモノオレート、アルキロースアミド系界面活性剤等を挙げることができる。 Specific examples of the activator include sorbitan monostearate, sorbitan monooleate, and alkylose amide surfactants.
さらに、重合開始剤としては、具体的にはアゾビスイソブチロニトリル、過酸化ベンゾイル等を挙げることができる。 Furthermore, specific examples of the polymerization initiator include azobisisobutyronitrile and benzoyl peroxide.
（紙塗工液）
本発明に係る流動性改質剤を紙塗工液に適用するに際しては、少なくとも顔料及びバインダーを含む混合原料に対して、該流動性改質剤を添加すればよく、また必要に応じてその他の添加剤等の各種成分を含有させてもよい。
これらの成分は、通常、紙塗工液に用いられている中から任意に選択使用でき、特に制限はない。
本発明の流動性改質剤の使用量は、顔料１００質量部当り０．００５〜１．０質量部とすることが好ましく、より好ましくは０．０１〜０．５質量部、さらに好ましくは０．０５〜０．３質量部である。
(Paper coating solution)
When the fluidity modifier according to the present invention is applied to a paper coating solution, the fluidity modifier may be added to the mixed raw material containing at least a pigment and a binder, and the others may be added as necessary. Various components such as additives may be included.
These components can be arbitrarily selected from those usually used in paper coating liquids, and are not particularly limited.
The use amount of the fluidity modifier of the present invention is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.5 part by mass, and still more preferably 0 per 100 parts by mass of the pigment. 0.05 to 0.3 parts by mass.
顔料としては、炭酸カルシウム、クレー、酸化チタン、シリカ、酸化亜鉛、水酸化アルミニウム、白土、レーキ、合成樹脂顔料から選択される１種もしくは２種以上が使用できる。 As the pigment, one or more selected from calcium carbonate, clay, titanium oxide, silica, zinc oxide, aluminum hydroxide, clay, lake, and synthetic resin pigment can be used.
また、バインダーとしては、スチレン−ブタジエン系共重合体、酢酸ビニル−ブタジエン系共重合体、エチレン−酢酸ビニル系共重合体、ブタジエン−メチルメタクリレート系共重合体、酢酸ビニル−ブチルアクリレート系共重合体、スチレン−無水マレイン酸系共重合体、イソブテン−無水マレイン酸系共重合体、アクリル酸−メチルメタクリレート系共重合体、酸化澱粉、エステル化澱粉、エーテル化澱粉、酵素変性澱粉、カゼイン、大豆蛋白等から選択される１種もしくは２種以上が使用できる。 The binder includes styrene-butadiene copolymer, vinyl acetate-butadiene copolymer, ethylene-vinyl acetate copolymer, butadiene-methyl methacrylate copolymer, vinyl acetate-butyl acrylate copolymer. Styrene-maleic anhydride copolymer, isobutene-maleic anhydride copolymer, acrylic acid-methyl methacrylate copolymer, oxidized starch, esterified starch, etherified starch, enzyme-modified starch, casein, soy protein 1 type, or 2 or more types selected from etc. can be used.
本発明の紙塗工液には、本発明の目的、効果が損なわれない範囲で、必要に応じて分散剤、増粘剤、消泡剤、耐水化剤、着色剤等の添加剤、改質剤等の通常、紙塗工液に用いられているものを適宜、配合添加してもよく、分散剤としては、例えばポリアクリル酸ナトリウム、ヘキサメタリン酸ナトリウム、ピロリン酸ナトリウム、アクリル酸−マレイン酸系共重合体のナトリウム塩等を挙げることができる。 In the paper coating solution of the present invention, additives such as a dispersant, a thickener, an antifoaming agent, a water-resistant agent, a colorant, and the like are modified and modified as necessary without departing from the object and effects of the present invention. The materials usually used in paper coating liquids such as a texture agent may be appropriately added and added. Examples of the dispersant include sodium polyacrylate, sodium hexametaphosphate, sodium pyrophosphate, acrylic acid-maleic acid Examples thereof include sodium salt of a copolymer.
（紙塗工液の特性）
本発明の紙塗工液は、添加剤として、前記したＷ／Ｏ型エマルジョンからなる流動性改質剤を配合しているため、保水性、流動性が向上している。
この保水性は、加圧脱水法によって測定した脱水量（加圧脱水量）の値に基づき評価することができる。
具体的には、リテンションメーターＡＡ−ＧＷＡ（カルテック・サイエンティフッィク社製）等を使用し、紙塗工液１０ｍｌ、圧力１５０ｋＰａ、加圧時間１５秒、温度２０℃の条件でろ紙に対する紙塗工液の脱水量（加圧脱水量（ｇ／ｍ２））を測定し、その測定値が小さいほど保水性が良好であると評価することができる。脱水量は用いる顔料、バインダーによって大きく異なり最適な数値を一義的に決めることはできない。
(Characteristics of paper coating solution)
Since the paper coating liquid of the present invention contains a fluidity modifier composed of the above-mentioned W / O emulsion as an additive, water retention and fluidity are improved.
This water retention can be evaluated based on the value of the amount of dehydration (pressure dehydration amount) measured by the pressure dehydration method.
Specifically, a paper for the filter paper is used under the conditions of a retention meter AA-GWA (produced by Caltech Scientific Co., Ltd.), a paper coating solution of 10 ml, a pressure of 150 kPa, a pressurization time of 15 seconds, and a temperature of 20 ° C. The dehydration amount (pressure dehydration amount (g / m 2 )) of the coating liquid is measured, and the smaller the measured value, the better the water retention. The amount of dehydration varies greatly depending on the pigment and binder used, and the optimum value cannot be determined uniquely.
また、ハイシェア（ＨＳ）条件下における紙塗工液の流動性は、ＨＳ粘度の測定値に基づき、評価することができる。
具体的には、ハイシェア（ＨＳ）粘度計を使用し、２２００ｒｐｍの回転数で、２０℃におけるＨＳ粘度（ｍＰａ・Ｓ）を測定する。一般的にはその測定値が小さいほど流動性が高いと評価することができるが、本発明のものはＨＳ粘度が高くても流動性が良い状態に維持できる。
本発明の紙塗工液においては、ＨＳ粘度は２５ｍＰａ・Ｓ以上が好ましい。特に感熱紙や感圧紙用塗工紙を得るために用いられる場合には、ＨＳ粘度は高いことが好ましいが、余り高いとストリーク、スクラッチ等の欠陥が生じやすくなるという問題もあり、該ＨＳ粘度は４０ｍＰａ・Ｓ以下であることが好ましい。
Further, the fluidity of the paper coating solution under high shear (HS) conditions can be evaluated based on the measured value of the HS viscosity.
Specifically, using a high shear (HS) viscometer, the HS viscosity (mPa · S) at 20 ° C. is measured at a rotational speed of 2200 rpm. In general, it can be evaluated that the smaller the measured value is, the higher the fluidity is, but the present invention can maintain a good fluidity even if the HS viscosity is high.
In the paper coating solution of the present invention, the HS viscosity is preferably 25 mPa · S or more. In particular, when used for obtaining thermal paper or coated paper for pressure sensitive paper, it is preferable that the HS viscosity is high, but if it is too high, defects such as streaks and scratches are liable to occur. Is preferably 40 mPa · S or less.
一方、紙塗工液の粘性は、Ｂ型粘度計の測定値に基づき評価することができ、具体的には、ＴＡＰＰＩ基準Ｔ６４８ Ｓｕ−７２に従って、６０ｒｐｍの回転で、２０℃におけるＢ型粘度（ｍＰａ・Ｓ）を測定し、その測定値が大きいほど粘性が高いと評価することができる。
本発明の紙塗工液においては、Ｂ型粘度（６０ｒｐｍ）が、低いことが好ましい。
On the other hand, the viscosity of the paper coating solution can be evaluated based on the measurement value of a B-type viscometer. Specifically, according to the TAPPI standard T648 Su-72, the viscosity of the B-type viscosity at 20 ° C. ( mPa · S) is measured, and the larger the measured value, the higher the viscosity.
In the paper coating solution of the present invention, the B-type viscosity (60 rpm) is preferably low.
本発明の前記特定の流動性改質剤を配合してなる紙塗工液はＢ型粘度が低く、ハイシェア粘度が高いという流動特性を有するものであるが、Ｂ型粘度が低いということは高速塗工が可能であることを意味し、またハイシェア粘度が高いということは紙基材に対する着量がアップし結果的に良好な品質の塗工紙が得られることを意味し、紙基材への紙塗工液の塗布において操業性及び塗工紙の品質の両面で好ましいものである。 The paper coating liquid obtained by blending the specific fluidity modifier of the present invention has flow characteristics such as low B type viscosity and high high shear viscosity, but low B type viscosity means high speed. This means that coating is possible, and high high shear viscosity means that the amount applied to the paper substrate is increased, resulting in a good quality coated paper. In the application of the paper coating solution, the operability and the quality of the coated paper are preferable.
本発明の紙塗工液を適用してなる塗工紙は、紙基材の少なくとも片面に、上記紙塗工液を塗工することにより得ることができる。
ここで得られる塗工紙は、保水性と流動性が維持され、高速塗工可能な紙塗工液（本発明の流動性改質剤含有）を用いてなるものであり、ストリーク、スクラッチ等の欠陥が生じることなく、白紙光沢、印刷光沢、ドライ及びウェットピック表面強度、耐ブリスター性、平滑性、インク受理性、網点再現性等にすぐれ、良好な表面特性を有する塗工紙である。
The coated paper to which the paper coating solution of the present invention is applied can be obtained by coating the paper coating solution on at least one side of the paper substrate.
The coated paper obtained here uses a paper coating solution (containing the fluidity modifier of the present invention) that maintains water retention and fluidity and can be coated at high speed, such as streak and scratch. The coated paper has excellent surface properties, such as white paper gloss, printing gloss, dry and wet pick surface strength, blister resistance, smoothness, ink acceptability, halftone dot reproducibility, etc. .
本発明の塗工紙を構成する紙基材としては、特に限定されるものではないが、例えば、上質紙、中質紙、板紙等を挙げることができる。また、紙塗工液の塗工とは、ブレードコーター、ロールコーター、エアナイフコーター等を用いる通常の方法により、紙基材の片面または両面に紙塗工液を薄膜状に塗布した後に乾燥処理して、所定の固形分付着量の塗工層を形成する操作をいう。形成される塗工層の固形分付着量は特に限定されないが２〜３０ｇ／ｍ２であることが好ましい。特に本発明においては、感熱紙や感圧紙といった特殊紙用に好適に用いることができる。 Although it does not specifically limit as a paper base material which comprises the coated paper of this invention, For example, a high quality paper, a medium quality paper, a paperboard etc. can be mentioned. In addition, the coating of the paper coating liquid is performed by applying a paper coating liquid in a thin film form on one or both sides of a paper substrate by a normal method using a blade coater, roll coater, air knife coater, etc. The operation of forming a coating layer having a predetermined solid content adhesion amount. Although the solid content adhesion amount of the coating layer to be formed is not particularly limited, it is preferably 2 to 30 g / m 2 . In particular, in the present invention, it can be suitably used for special paper such as thermal paper and pressure sensitive paper.
以下に本発明を実施例に基づいて具体的に説明するが、本発明はこれに限定されるものではない。なお、各物性は下記のようにして測定したものである。
なお、「部」は「質量部」を示す。
Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. Each physical property is measured as follows.
“Part” means “part by mass”.
［Ｂ型粘度］
ＴＡＰＰＩ基準Ｔ６４８ Ｓｕ−７２に従って、６ｒｐｍ及び６０ｒｐｍの回転数で、２０℃におけるＢ型粘度（ｍＰａ・ｓ）を測定した。
［ＨＳ粘度］
ハイシェア粘度計（日本精機（株）製）を使用し、２２００ｒｐｍの回転で、２０℃におけるハイシェア粘度（ｍＰａ・ｓ）を測定した。
［加圧脱水量（保水性）］
加圧脱水法に従い、リテンションメーター ＡＡ−ＧＷＲ（カルテック・サイエンティフィック（Ｋａｌｔｅｃ Ｓｃｉｅｎｔｉｆｉｃ）社製）を使用し、紙塗工液１０ｍｌ、圧力１５０ｋＰａ、加圧時間１５秒、温度２０℃の各条件で濾紙に対する紙塗工液の脱水量（加圧脱水量（ｇ／ｍ２））を測定した。
なお、加圧脱水量の測定値が小さいほど保水性が良好であることを示す。
[B type viscosity]
According to TAPPI standard T648 Su-72, B-type viscosity (mPa · s) at 20 ° C. was measured at 6 rpm and 60 rpm.
[HS viscosity]
Using a high shear viscometer (manufactured by Nippon Seiki Co., Ltd.), the high shear viscosity (mPa · s) at 20 ° C. was measured at a rotation of 2200 rpm.
[Pressure dewatering amount (water retention)]
According to the pressure dehydration method, using a retention meter AA-GWR (manufactured by Kaltec Scientific) under the following conditions: paper coating solution 10 ml, pressure 150 kPa, pressurization time 15 seconds, temperature 20 ° C. The amount of paper coating liquid dehydrated with respect to the filter paper (pressure dewatered amount (g / m 2 )) was measured.
In addition, it shows that water retention is so favorable that the measured value of the pressure dehydration amount is small.
（本発明の流動性改質剤のＷ／Ｏ型エマルジョンの合成）
室温下で、内容積３００ｃｃのフラスコに、鉱物油（製品名：アイソパー、エクソン化学（株）製、一般化学名：イソパラフィン系炭化水素）７６．１３部と活性剤（アミゾールＯＤＥ３．０部、アデカトールＤＢ−１０８０、５．４６部、ソルゲン４０、５．４１部）を仕込み、均一に混合し窒素置換した。
この混合物に、水に溶解させたアクリル酸ナトリウムとアクリルアミド（アクリル酸ナトリウム４３．４４部、アクリルアミド７６．６５部、水９０部）を添加、攪拌しプレエマルジョンを合成した。
このプレエマルジョン生成物の１／５量を窒素雰囲気下、内容積５００ｃｃの反応容器に入れ、これに重合開始剤の２，２’−アゾビス（２，４−ジメチル）バレロニトリル０．０１部を添加し、温度５０〜５５℃、回転数１００ｒｐｍで１０分間攪拌した。
次に、プレエマルジョン生成物の４／５量と重合開始剤の２，２’−アゾビス（２，４−ジメチル）バレロニトリル０．０３部を温度５０〜５５℃、攪拌下（３００ｒｐｍ）にて少量ずつ連続的に２時間を要して添加した。
系内の温度を６０℃未満（５８℃）に維持し、３０分間攪拌した後、８０℃まで昇温し、３０分間熟成を行なった。
このようにして得られた反応生成物は、前記した式（１）で示されるアクリル系共重合体（重量平均分子量１．５×１０７、ｍ＝７０、ｎ＝３０）のＷ／Ｏ型エマルジョンであることを極限粘度測定、およびアニオン要求量、およびＩＲにより確認した。
(Synthesis of W / O type emulsion of fluidity modifier of the present invention)
At room temperature, in a flask with an internal volume of 300 cc, 76.13 parts of mineral oil (product name: Isopar, manufactured by Exxon Chemical Co., Ltd., general chemical name: isoparaffin hydrocarbon) and activator (Amisole ODE 3.0 parts, Adecatol) DB-1080, 5.46 parts, Sorgen 40, 5.41 parts) were charged, mixed uniformly, and purged with nitrogen.
To this mixture, sodium acrylate and acrylamide (sodium acrylate 43.44 parts, acrylamide 76.65 parts, water 90 parts) dissolved in water were added and stirred to synthesize a pre-emulsion.
1/5 of this pre-emulsion product was placed in a reaction vessel having an internal volume of 500 cc under a nitrogen atmosphere, and 0.01 part of 2,2′-azobis (2,4-dimethyl) valeronitrile as a polymerization initiator was added thereto. The mixture was added and stirred at a temperature of 50 to 55 ° C. and a rotation speed of 100 rpm for 10 minutes.
Next, 4/5 amount of the pre-emulsion product and 0.03 part of 2,2′-azobis (2,4-dimethyl) valeronitrile as a polymerization initiator were stirred at a temperature of 50 to 55 ° C. (300 rpm). It was added in small portions continuously over 2 hours.
The temperature in the system was maintained at less than 60 ° C. (58 ° C.), stirred for 30 minutes, then heated to 80 ° C. and aged for 30 minutes.
The reaction product thus obtained was a W / O type of acrylic copolymer (weight average molecular weight 1.5 × 10 7 , m = 70, n = 30) represented by the above formula (1). It was confirmed by an intrinsic viscosity measurement, an anion requirement, and IR that it was an emulsion.
実施例１〜２
クレー７０部、重質炭酸カルシウム３０部、スチレン−ブタジエン共重合体ラテックス１０部（固形分）、リン酸化デンプン１部、分散剤（ソマール（株）製、製品名ＳＤＡ−４０Ｋ）０．１部（固形分）を混合し、全体の固形分が約６２質量％になるように水を加えたのち、これに上記で合成したアクリル系共重合体のＷ／Ｏ型エマルジョンよりなる流動性改質剤を０．０４部（固形分）、または０．０８部（固形分）となるように加え均一に混合することにより、塗工液を調製した。
これらの塗工液の物性を表１に示す。
Examples 1-2
70 parts of clay, 30 parts of heavy calcium carbonate, 10 parts of styrene-butadiene copolymer latex (solid content), 1 part of phosphorylated starch, 0.1 part of dispersant (product name SDA-40K, manufactured by Somaar Co., Ltd.) (Solid content) is mixed, water is added so that the total solid content is about 62% by mass, and then the fluidity modification comprising the W / O emulsion of the acrylic copolymer synthesized above is added thereto. The coating liquid was prepared by adding an agent so that it might become 0.04 part (solid content) or 0.08 part (solid content), and mixing uniformly.
Table 1 shows the physical properties of these coating solutions.
比較例１〜２
実施例１において、Ｗ／Ｏ型エマルジョンの代りに、メタクリル酸−アクリル酸エチル共重合体（モル比６０：４０、重量平均分子量２，５００，０００）のＯ／Ｗ型エマルジョンを表１に示すような量を用いた以外は、実施例１と同様にして、塗工液を調製した。これらの塗工液の物性を表１に示す。
Comparative Examples 1-2
In Example 1, instead of the W / O type emulsion, an O / W type emulsion of a methacrylic acid-ethyl acrylate copolymer (molar ratio 60:40, weight average molecular weight 2,500,000) is shown in Table 1. A coating solution was prepared in the same manner as in Example 1 except that such an amount was used. Table 1 shows the physical properties of these coating solutions.
比較例３〜４
実施例１において、Ｗ／Ｏ型エマルジョンの代りに、メタクリル酸−アクリル酸エチル共重合体（モル比５０：５０、重量平均分子量３，０００，０００）のＯ／Ｗ型エマルジョンを表１に示すような量を用いた以外は、実施例１と同様にして、塗工液を調製した。これらの塗工液の物性を表１に示す。
Comparative Examples 3-4
In Example 1, an O / W emulsion of a methacrylic acid-ethyl acrylate copolymer (molar ratio 50:50, weight average molecular weight 3,000,000) is shown in Table 1 instead of the W / O emulsion. A coating solution was prepared in the same manner as in Example 1 except that such an amount was used. Table 1 shows the physical properties of these coating solutions.
比較例５〜６
実施例１において、Ｗ／Ｏ型エマルジョンの代りに、水で希釈することにより転相し水溶液に変えた以外は、実施例１と同様にして、塗工液を調製した。これらの塗工液の物性を表１に示す。
Comparative Examples 5-6
In Example 1, a coating solution was prepared in the same manner as in Example 1 except that the phase was changed by diluting with water instead of the W / O type emulsion to change to an aqueous solution. Table 1 shows the physical properties of these coating solutions.
表２に各実施例及び比較例の紙塗工液の処方についてまとめて示す。 Table 2 summarizes the prescriptions of the paper coating solutions of each Example and Comparative Example.
上記処方の固形分：約６２質量％
これに流動性改質剤を添加
流動性改質剤の添加量（部）：
顔料（クレーと重炭酸カルシウム）１００部に対する固形分量
Solid content of the above formulation: about 62% by mass
Fluidity modifier added to this Amount of fluidity modifier added (parts):
Solid content per 100 parts pigment (clay and calcium bicarbonate)
表１に示すように、流動性改質剤を同じ量用いた実施例２と比較例１、３との対比により、本発明の流動性改質剤を用いた紙塗工液は、比較例１、３のそれに比べてＢ型粘度が低く、ＨＳ粘度が高いという流動性に優れていることが分かる。また実施例２における流動性改質剤の使用量を半分にした実施例１においても、その優れた流動性は十分に保持されていることが分かる。さらにＨＳ粘度を高くするための流動性改質剤の量を比較例１、３の２倍用いた比較例２、４はＢ型粘度が著しく上昇してしまい、ＨＳ粘度も高くなるものの不十分であった。さらに、実施例１、２で用いた流動性改質剤を転相した水溶液からなる流動性改質剤を用いた比較例５、６の紙塗工液は、Ｂ型粘度は低くなるが、ＨＳ粘度においては高くなるものの満足し得るものではなかった。
このことから、本発明の流動性改質剤は少量においても紙基材に塗工液を塗布する際にはロールコーターでの塗工において本発明の紙塗工液を用いることによって、塗工の高速化が達成でき、塗工紙の生産性が向上すると共に、得られた塗工紙は嵩高で平滑性に優れた高品質のものであることが分かる。
As shown in Table 1, the paper coating liquid using the fluidity modifier of the present invention is a comparative example by comparing Example 2 and Comparative Examples 1 and 3 using the same amount of fluidity modifier. It can be seen that the B-type viscosity is lower than that of 1 and 3, and that the HS viscosity is high, the fluidity is excellent. It can also be seen that the excellent fluidity is sufficiently maintained in Example 1 in which the amount of the fluidity modifier used in Example 2 is halved. Further, Comparative Examples 2 and 4 in which the amount of the fluidity modifier for increasing the HS viscosity is twice that of Comparative Examples 1 and 3 are not sufficient although the B-type viscosity is remarkably increased and the HS viscosity is increased. Met. Furthermore, the paper coating liquids of Comparative Examples 5 and 6 using a fluidity modifier comprising an aqueous solution obtained by phase-inversion of the fluidity modifier used in Examples 1 and 2 have a low B-type viscosity. Although the HS viscosity was high, it was not satisfactory.
Therefore, the fluidity modifier of the present invention can be applied by using the paper coating solution of the present invention in the coating with a roll coater when applying the coating solution to the paper substrate even in a small amount. It can be seen that the speed of the coating paper can be increased, the productivity of the coated paper is improved, and the obtained coated paper is bulky and has high quality with excellent smoothness.
Claims (4)
A coated paper, wherein the paper coating liquid according to claim 3 is applied to a paper substrate.
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| WO2007142271A1 (en) * | 2006-06-07 | 2007-12-13 | Somar Corporation | Paper coating liquid and coated paper using the same |
| JP2010053481A (en) * | 2008-08-28 | 2010-03-11 | Oji Paper Co Ltd | Coated white paperboard |
| WO2010114467A1 (en) * | 2009-04-02 | 2010-10-07 | Korsnäs AB (publ) | A pigment coated paperboard adapted for sterilizable packages |
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