JP5273653B2 - Papermaking chemicals and methods of use - Google Patents
Papermaking chemicals and methods of use Download PDFInfo
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- JP5273653B2 JP5273653B2 JP2008249381A JP2008249381A JP5273653B2 JP 5273653 B2 JP5273653 B2 JP 5273653B2 JP 2008249381 A JP2008249381 A JP 2008249381A JP 2008249381 A JP2008249381 A JP 2008249381A JP 5273653 B2 JP5273653 B2 JP 5273653B2
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
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- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 239000011306 natural pitch Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- IACHBBYPUKLZPO-UHFFFAOYSA-N triethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCCNC(=O)C=C IACHBBYPUKLZPO-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Abstract
Description
本発明は、製紙用薬剤およびその使用方法に関し、詳しくは特定の二種類のカチオン性単量体、イタコン酸、（メタ）アクリル酸、（メタ）アクリルアミドの各構成単位を有する水溶性高分子からなる製紙用薬剤に関する。また前記水溶性高分子を濾水性向上剤あるいは歩留向上剤、層間強度向上剤あるいは紙力増強剤あるいは製紙における欠点発生防止剤として用いた応用例、さらに濾水性向上剤あるいは歩留向上剤と他の薬剤とを併用した製紙方法にも関する。 The present invention relates to a papermaking agent and a method for using the same, and more specifically, from a water-soluble polymer having respective structural units of two specific types of cationic monomers, itaconic acid, (meth) acrylic acid, and (meth) acrylamide. It is related with the chemical | medical agent for papermaking. Application examples in which the water-soluble polymer is used as a drainage improver, a yield improver, an interlaminar strength improver, a paper strength enhancer, or a defect generation preventing agent in papermaking, and a drainage improver or a yield improver It also relates to a papermaking method using other drugs in combination.
抄紙工程におけるワイヤー上の紙料および灰分の歩留まりを向上させることは、排水負荷の軽減、流失原料の削減による製造コストの低減、紙の二面性改善などの紙品質の向上、生産性の向上などから重要な意味を有している。そのため従来より歩留向上剤の開発研究も継続的に行われてきているが、その間、多様な水溶性高分子を応用した例が提案され、またジュアル処方として水溶性高分子との組み合わせとなる無機粒子や有機マイクロパーティクルも提案されている。 Improving the yield of paper and ash on the wire in the papermaking process can be achieved by reducing the drainage load, reducing manufacturing costs by reducing lost materials, improving paper quality, such as improving paper duality, and improving productivity. It has an important meaning. For this reason, research and development of yield improvers has been ongoing, but during that time, various water-soluble polymer applications have been proposed and combined with water-soluble polymers as dual formulations. Inorganic particles and organic microparticles have also been proposed.
一方、新聞印刷用紙の製造における近年の技術動向の一つとして、環境に対する意識の向上やコストダウンなどを背景とした、新聞印刷用紙への古紙配合率の増加を挙げることができる。この結果、製紙用水中には種々の溶存物質あるいは微細な粒子状物質が存在するようになる。これらの物質は、パルプ製造時に由来するものと、古紙製造時に由来するものとがある。すなわちパルプ製造時に由来するものとしては、リグニンスルホネート、リグニン分解生成物、木材抽出物、セルロース誘導体（例えば、ヘミセルロース）などである。また古紙製造時に由来するものとしては、サイジング剤、分散剤、染料、蛍光漂白剤、コーティングバインダー、湿潤剤、珪酸ナトリウムなどである。さらに導入する工業用水などにもフミン酸やカルシウム成分なども混入する。 On the other hand, one of recent technological trends in the production of newspaper printing paper is an increase in the ratio of used paper to newspaper printing paper against the background of increased environmental awareness and cost reduction. As a result, various dissolved substances or fine particulate substances are present in the papermaking water. Some of these substances are derived during pulp production and others are derived during waste paper manufacture. That is, as derived from pulp production, lignin sulfonate, lignin degradation product, wood extract, cellulose derivative (eg, hemicellulose) and the like. In addition, the sizing agent, dispersant, dye, fluorescent bleaching agent, coating binder, wetting agent, sodium silicate, and the like are derived from the production of used paper. Furthermore, humic acid and calcium components are mixed in industrial water to be introduced.
このうちアニオントラッシュと呼ばれる溶存性あるいは親水性のアニオン性成分、すなわちホワイト顔料、分散剤、改質でんぷん、カルボキシメチルセルロース、リグニンスルホネート、リグニン分解生成物、ヘミセルロースなどは、一般的な低分子量カチオン性水溶性高分子物質により処理することによって歩留率や濾水性はかなりの程度改善される。しかし水に溶解しない疎水的な成分は、人工的なものはスティッキー、木材など天然に由来するものはピッチと呼ばれ区別している。すなわちは木材抽出物、サイジング剤、あるいはコーティングバインダーなどは、微細なコロイド粒子として製紙原料中に分散している場合は、悪影響は少ない。しかしこれらのコロイドは表面電荷が低く、アニオン性に弱く解離している場合、あるいは解離もしていない場合もあり、基本的に不安定な物質である。したがって温度、シェア、ｐＨ、あるいはピッチ障害を抑制するために添加される有機や無機のカチオン性物質などによってコロイドが破壊され粗大化する。その結果、表面が粘着性を帯びているため電荷を調節しただけでは、それらが紙中に抄きこまれた場合、またワイヤー、フェルト、ローラーあるいはドライヤーの各表面に再付着し、一定以上の大きさに成長すると製造中の成紙に付着し、欠点などの障害を引き起こす。またこれら疎水的な成分は、カチオン性水溶性高分子物質により処理し、粒子系を粗大化させてしまうこともある。そうすると上記の障害はより顕著に発生し、カチオン性水溶性高分子物質などの処理剤が逆効果になる場合もあるので注意を要する。 Of these, soluble or hydrophilic anionic components called anionic trash, namely white pigments, dispersants, modified starches, carboxymethylcellulose, lignin sulfonate, lignin degradation products, hemicellulose, etc. Yield rate and drainage can be improved to a considerable extent by treatment with a conductive polymer substance. However, hydrophobic components that do not dissolve in water are distinguished by being called sticky for artificial ones and pitch for natural ones such as wood. That is, the wood extract, the sizing agent, the coating binder or the like has little adverse effect when dispersed as fine colloidal particles in the papermaking raw material. However, these colloids have a low surface charge and are weakly anionic and dissociated or may not be dissociated and are basically unstable substances. Accordingly, the colloid is destroyed and coarsened by an organic or inorganic cationic substance added to suppress temperature, shear, pH, or pitch disturbance. As a result, the surface is sticky, so if the charge is only adjusted, they will be re-attached to the surface of the wire, felt, roller or dryer when they are baked into the paper, and the size will exceed a certain level. When it grows up, it adheres to the paper being manufactured and causes problems such as defects. Further, these hydrophobic components may be treated with a cationic water-soluble polymer substance to coarsen the particle system. In such a case, the above-described obstacles are more noticeably generated, and a treatment agent such as a cationic water-soluble polymer substance may have an adverse effect, so care must be taken.
例えば特許文献１は、天然ピッチトラブル抑制のためジメチルジアリルアンモニウム塩化物／アクリル酸／（場合によっては、アクリル酸アルキルエステル類）共重合物を抄紙系のウェットエンドに添加する方法が開示されている。また、パルプ製造の漂白工程アルカリ抽出において、原料木材に由来するパルプ中のピッチを除去する方法として、水溶性の不飽和カルボン酸と疎水性単量体との共重合体を、漂白後のパルプスラリ−が次ぎのアルカリ抽出塔に入る前に添加することを開示している（特許文献２）。 For example, Patent Document 1 discloses a method for adding a dimethyldiallylammonium chloride / acrylic acid / (optionally acrylic acid alkyl ester) copolymer to a paper-making wet end to suppress natural pitch trouble. . In addition, as a method of removing pitch in pulp derived from raw wood in the bleaching step alkali extraction of pulp production, a copolymer of a water-soluble unsaturated carboxylic acid and a hydrophobic monomer is used as a pulp slurry after bleaching. -Is added before entering the next alkali extraction tower (Patent Document 2).
新聞用紙原料は、機械パルプや古紙を使用するため上記のようなピッチあるいはステイッキーの存在が多いため、新聞用紙は、１０年ほど前までは酸性抄紙が常識的であった。ところが、この数年新聞古紙のリサイクル率がさらに上昇するにつれ、古紙中に広告用のチラシの比率が増加してきた。このチラシ中には填量料として炭酸カルシウムが大量に含有している。従来、新聞用紙を酸性で抄紙していた場合は、前記炭酸カルシウムを酸により中和した後、抄紙する工程を採用していた。しかし、炭酸カルシウムが多量なため、酸の使用量が非常に多く製造コストにも影響が出始めている。また、中和することにより、製紙原料スラリ−中に溶解塩類が多量に共存するようになり、紙の品質あるいは製紙工程においての影響が懸念される。このような状況に対応するため中性新聞印刷用紙の抄紙法として極限粘度法による重量平均分子量が１，５００万以上のエマルション型のカチオン性ポリアクリルアミド系物質を紙料に添加した後、アニオン性水溶性高分子、コロイダルシリカおよびベントナイトから選択される一種以上を添加する方法が提案されている（特許文献３）。 Since newsprint raw materials use mechanical pulp and waste paper, there are many pitches or stickies as described above, so it was common sense for newsprint to be acid paper until about 10 years ago. However, as the recycling rate of used newspapers has increased further in recent years, the ratio of advertising flyers in used paper has increased. This flyer contains a large amount of calcium carbonate as a filler. Conventionally, in the case where newsprint paper is made with an acid, a process of making paper after neutralizing the calcium carbonate with an acid has been adopted. However, due to the large amount of calcium carbonate, the amount of acid used is very large and the production cost is beginning to be affected. Further, by neutralization, a large amount of dissolved salts coexist in the papermaking raw material slurry, and there is a concern about the influence on the quality of paper or the papermaking process. In order to cope with this situation, an emulsion type cationic polyacrylamide material having a weight average molecular weight of 15 million or more by the intrinsic viscosity method as a paper making method for neutral newspaper printing paper is added to the stock, and then anionic A method of adding one or more selected from water-soluble polymers, colloidal silica, and bentonite has been proposed (Patent Document 3).
一方、紙力増強剤は通常、アニオン性と両性が使用されている。このうち、両性の紙力増強剤は、従来アクリルアミドとＮ、Ｎ−ジアルキルアミノ（メタ）アクリレ−トあるいはＮ，Ｎ−ジアルキルアミノ（メタ）アクリルアミドなどと（メタ）アクリル酸による共重合体が一般的に使用されてきた。また、これに架橋剤としてＮ、Ｎ−メチレンビスアクリルアミドなどが共重合され、さらに最近では、Ｎ，Ｎ−ジメチルアクリルアミドが共重合され特異な溶液物性を示す高分子からなる紙力増強剤が開発されている。紙力増強効果は、セルロ−ス分子中の水酸基と紙力増強剤中の水素結合力を有する側鎖との水素結合力に起因するものである。またこれに紙力増強剤として使用される高分子の分子量も効果に影響してくる。すなわち一定の分子量以上、即ち、数１０万以上の分子量がないと紙力増強剤としての効果は顕著ではない。従来使用されてきたウェットエンドに添加される紙力増強剤の分子量は、数十万〜１００万程度であり、これに前記の架橋性単量体が共重合されたタイプは、２００万〜５００万に及ぶ。また製紙プロセスの現状を見てみると、デンプン系紙力増強剤はコストその他のメリットから多くの製紙現場で使用され、これを前記のような分散重合タイプからなるアクリル系紙力増強剤に完全に置き換えることは、必ずしも得策ではないと考えられる。デンプン系紙力増強剤の定着効果を高めるため高分子量の分散型アクリル系紙力増強剤を併用する方法が提案されている（特許文献４）。またジメチルアミノエチルアクリレートの塩化メチルによる四級塩、ジメチルアミノエチルアクリレートのベンジルクロライド四級塩、イタコン酸かアクリル酸のどちらか一種およびアクリルアミドを共重合した両性高分子が濾水性あるいは歩留向上剤として使用されている例がある（特許文献５）。さらにジメチルアミノエチルアクリレート四級塩、ジメチルアミノエチルアクリレートのベンジルクロライド四級塩、イタコン酸、アクリル酸およびアクリルアミドを共重合した両性高分子の例があるが（特許文献６）、製紙用薬剤へ応用の記載はない。 On the other hand, an anionic property and an amphoteric property are usually used for the paper strength enhancer. Of these, amphoteric paper strength enhancers are conventionally copolymers of acrylamide and N, N-dialkylamino (meth) acrylate or N, N-dialkylamino (meth) acrylamide and (meth) acrylic acid. Have been used. In addition, N, N-methylenebisacrylamide and the like are copolymerized as a cross-linking agent, and more recently, a paper strength enhancer composed of a polymer exhibiting unique solution properties has been developed by copolymerizing N, N-dimethylacrylamide. Has been. The paper strength enhancing effect is due to the hydrogen bonding strength between the hydroxyl group in the cellulose molecule and the side chain having hydrogen bonding strength in the paper strength enhancing agent. The molecular weight of the polymer used as a paper strength enhancer also affects the effect. That is, the effect as a paper strength enhancer is not remarkable unless there is a certain molecular weight or more, that is, a molecular weight of several hundred thousand or more. The molecular weight of the paper strength enhancer added to the wet end that has been conventionally used is about several hundred thousand to one million, and the type in which the crosslinkable monomer is copolymerized with this has two million to 500 million. Ten thousand. Looking at the current state of the papermaking process, starch-based paper strength enhancers are used in many papermaking sites due to cost and other advantages. Replacing with is not necessarily a good idea. In order to enhance the fixing effect of the starch-based paper strength enhancer, a method using a high molecular weight dispersed acrylic paper strength enhancer has been proposed (Patent Document 4). In addition, quaternary salt of dimethylaminoethyl acrylate with methyl chloride, benzyl chloride quaternary salt of dimethylaminoethyl acrylate, itaconic acid or acrylic acid, and an amphoteric polymer copolymerized with acrylamide is a drainage or retention improver. (Patent Document 5). Furthermore, there are examples of amphoteric polymers obtained by copolymerizing dimethylaminoethyl acrylate quaternary salt, benzyl chloride quaternary salt of dimethylaminoethyl acrylate, itaconic acid, acrylic acid and acrylamide (Patent Document 6). There is no description.
上記のように近年においては資源の節約、リサイクル意識の高まりにより紙・板紙のリサイクルの比率が増加し、古紙が製紙原料へ多量に混入してきている。
新聞用紙においては、従来の単なる古紙新聞紙が混入するだけでなく、チラシ類が選別されることなく混入する。チラシ類は、塗工紙である場合がほぼ全てであり、それに伴い炭酸カルシウム、顔料、糊料、ラテクッス類などが一緒に入り、更に古紙配合率増加に伴う用水悪化などは、ワイヤー上の歩留率および紙質低下の方向に作用することは避けられない。そのため既存のジメチルアミノエチルアクリレートの四級化物とアクリルアミドの共通重合物によるカチオン当量と分子量の調節だけでは対応が難しくなってきている。従ってこれに替わる新しい組成の歩留向上剤、紙力増強剤あるいはピッチ障害を防止する成紙上の欠点発生防止剤など製紙用薬剤の開発が求められていた。
As described above, in recent years, the ratio of paper and paperboard recycling has increased due to resource conservation and increased awareness of recycling, and a large amount of used paper has been mixed into papermaking raw materials.
In newspaper paper, not only conventional mere waste paper but also leaflets are mixed without being sorted. Flyers are almost all coated papers, and calcium carbonate, pigments, glues, latexes, etc. are included together with it, and the deterioration of water usage due to an increase in the ratio of used paper is a step on the wire. It is unavoidable to act in the direction of the yield and paper quality. For this reason, it is difficult to cope with the problem only by adjusting the cation equivalent and the molecular weight of the existing quaternized product of dimethylaminoethyl acrylate and a common polymer of acrylamide. Accordingly, there has been a demand for the development of a papermaking agent such as a yield improving agent having a new composition, a paper strength enhancing agent, or a defect preventing agent for preventing the occurrence of defects on the paper.
本発明の課題は、古紙配合率が増加しても歩留が低下せず、紙質向上が期待できる新しい組成の製紙用薬剤を提供することにある。 An object of the present invention is to provide a papermaking agent having a new composition that can be expected to improve paper quality without decreasing the yield even when the ratio of used paper increases.
上記課題を解決するため鋭意検討を重ねた結果、以下に述べるような発明に到達した。すなわち請求項１の発明は、下記一般式（１）で表される単量体が２〜４０モル％、下記一般式（２）で表される単量体が２〜５０モル％、イタコン酸１〜３０モル％、（メタ）アクリル酸１〜３０モル％、（メタ）アクリルアミド０〜９４モル％の各単量体を重合した重量平均分子量が１６００万〜３０００万の水溶性高分子からなる濾水性向上剤あるいは歩留向上剤である。
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキル基あるいはアルコキシル基であり、同種でも異種でも良い。Ａ１はＯまたはＮＨ、Ｂ１は炭素数２〜４のアルキレン基、Ｘ１ −は陰イオンをそれぞれ表す。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、Ｒ７は水素、炭素数１〜３のアルキル基であり、同種でも異種でも良い。Ａ２はＯまたはＮＨ、
Ｂ２は炭素数２〜４のアルキレン基、Ｘ２ −は陰イオンをそれぞれ表す。
As a result of intensive studies to solve the above-mentioned problems, the inventors have reached the invention as described below. That is, the invention of claim 1 is that the monomer represented by the following general formula (1) is 2 to 40 mol%, the monomer represented by the following general formula (2) is 2 to 50 mol%, and itaconic acid. 1 to 30 mol%, (meth) acrylic acid 1 to 30 mol%, and (meth) acrylamide 0 to 94 mol% polymerized each water-soluble polymer having a weight average molecular weight of 16 to 30 million It is a drainage improver or a yield improver .
R 1 is hydrogen or a methyl group, and R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, which may be the same or different. A 1 is O or NH, B 1 is an alkylene group having 2 to 4 carbon atoms, X 1 - represents each an anion.
R 4 is hydrogen or a methyl group, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, R 7 is hydrogen and an alkyl group having 1 to 3 carbon atoms, and may be the same or different. A 2 is O or NH,
B 2 represents an alkylene group having 2 to 4 carbon atoms, and X 2 − represents an anion.
請求項２の発明は、下記一般式（１）で表される単量体２〜１０モル％、下記一般式（２）で表される単量体２〜１０モル％、イタコン酸１〜２０モル％、（メタ）アクリル酸１〜２０モル％、（メタ）アクリルアミド４０〜９４モル％の各構成単位からなる層間強度向上剤あるいは紙力増強剤である。
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキル基あるいはアルコキシル基であり、同種でも異種でも良い。Ａ１はＯまたはＮＨ、Ｂ１は炭素数２〜４のアルキレン基、Ｘ１ −は陰イオンをそれぞれ表す。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、Ｒ７は水素、炭素数１〜３のアルキル基であり、同種でも異種でも良い。Ａ２はＯまたはＮＨ、
Ｂ２は炭素数２〜４のアルキレン基、Ｘ２ −は陰イオンをそれぞれ表す。
Invention of Claim 2 is 2-10 mol% of monomer represented by following General formula (1), 2-10 mol% of monomer represented by following General formula (2), Itaconic acid 1-20 It is an interlaminar strength improver or paper strength enhancer composed of respective structural units of mol%, (meth) acrylic acid 1 to 20 mol%, and (meth) acrylamide 40 to 94 mol%.
R 1 is hydrogen or a methyl group, and R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, which may be the same or different. A 1 is O or NH, B 1 is an alkylene group having 2 to 4 carbon atoms, X 1 - represents each an anion.
R 4 is hydrogen or a methyl group, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, R 7 is hydrogen and an alkyl group having 1 to 3 carbon atoms, and may be the same or different. A 2 is O or NH,
B 2 represents an alkylene group having 2 to 4 carbon atoms, and X 2 − represents an anion.
請求項３の発明は、下記一般式（１）で表される単量体２〜３０モル％、下記一般式（２）で表される単量体２〜５０モル％、イタコン酸１〜１０モル％、（メタ）アクリル酸１〜１０モル％、（メタ）アクリルアミド０〜９４モル％の各構成単位からなる製紙における欠点発生防止剤である。
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキル基あるいはアルコキシル基であり、同種でも異種でも良い。Ａ１はＯまたはＮＨ、Ｂ１は炭素数２〜４のアルキレン基、Ｘ１ −は陰イオンをそれぞれ表す。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、Ｒ７は水素、炭素数１〜３のアルキル基であり、同種でも異種でも良い。Ａ２はＯまたはＮＨ、
Ｂ２は炭素数２〜４のアルキレン基、Ｘ２ −は陰イオンをそれぞれ表す。
A third aspect of the present invention, the monomer 2-30 mole% represented by the following following general formula (1), monomer 2 to 50 mole% represented by the following following general formula (2), itaconic acid 1 10% by mole, 1 to 10% by mole of (meth) acrylic acid, and 0 to 94% by mole of (meth) acrylamide.
R 1 is hydrogen or a methyl group, and R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, which may be the same or different. A 1 is O or NH, B 1 is an alkylene group having 2 to 4 carbon atoms, X 1 - represents each an anion.
R 4 is hydrogen or a methyl group, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, R 7 is hydrogen and an alkyl group having 1 to 3 carbon atoms, and may be the same or different. A 2 is O or NH,
B 2 represents an alkylene group having 2 to 4 carbon atoms, and X 2 − represents an anion.
請求項４の発明は、請求項１に記載の水溶性高分子と、下記一般式（３）で表わされる単量体から選択される一種以上と（メタ）アクリルアミドとの共重合体、コロイダルシリカおよびベントナイトから選択される一種以上とを併用し、抄紙前の製紙原料中に添加し抄紙することを特徴とする製紙方法。
Ｒ８は水素またはＣＨ２ＣＯＯＹ２、ＱはＳＯ３、Ｃ６Ｈ４ＳＯ３、
ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３、Ｃ６Ｈ４ＣＯＯあるいはＣＯＯ、Ｒ９は水素、メチル基またはＣＯＯＹ３であり、Ｙ１、Ｙ２は水素または陽イオンをそれぞれ表わす。
The invention of claim 4 is a copolymer, colloidal silica, of the water-soluble polymer of claim 1 and one or more selected from monomers represented by the following general formula (3) and (meth) acrylamide And one or more selected from bentonite, and added to the papermaking raw material before papermaking to make paper.
R 8 is hydrogen or CH 2 COOY 2 , Q is SO 3 , C 6 H 4 SO 3 ,
CONHC (CH 3 ) 2 CH 2 SO 3 , C 6 H 4 COO or COO, R 9 is hydrogen, a methyl group or COOY 3 , and Y 1 and Y 2 each represent hydrogen or a cation.
請求項５の発明は、前記製紙原料が中性新聞用紙のものであることを特徴とする請求項４に記載の製紙方法である。 The invention according to claim 5 is the paper manufacturing method according to claim 4 , wherein the papermaking raw material is neutral newsprint paper.
本発明の製紙用薬剤は、（メタ）アクリル系四級アンモニウム塩、ベンジル基を有する（メタ）アクリル系四級アンモニウム塩、イタコン酸、（メタ）アクリル酸、（メタ）アクリルアミドの各構成単位を有する水溶性高分子からなる。その結果、通常の四級アンモニウム塩基と疎水基を有する四級アンモニウム塩基、通常のアニオン性単量体と二個のアニオン性基を有する単量体の各構成単位が分子中に存在するため、古紙配合率の上昇している今日の製紙原料事情にも対応し、優れた歩留性能、紙力増強性能、製紙における欠点発生防止性能などを有する。 The papermaking chemical of the present invention comprises (meth) acrylic quaternary ammonium salt, (meth) acrylic quaternary ammonium salt having a benzyl group, itaconic acid, (meth) acrylic acid, and (meth) acrylamide. It consists of a water-soluble polymer. As a result, since each constituent unit of a normal quaternary ammonium base and a quaternary ammonium base having a hydrophobic group, a normal anionic monomer and a monomer having two anionic groups is present in the molecule, Responding to today's papermaking raw material situation where the ratio of used paper is increasing, it has excellent yield performance, paper strength enhancement performance, and defect generation prevention performance in papermaking.
本発明の製紙用薬剤は、下記一般式（１）で表される単量体、一般式（２）で表される単量体、イタコン酸、（メタ）アクリル酸、（メタ）アクリルアミドの各構成単位を有する水溶性高分子からなる。初めに重合構成に必要な単量体に関して説明する。 The papermaking chemicals of the present invention include monomers represented by the following general formula (1), monomers represented by the general formula (2), itaconic acid, (meth) acrylic acid, and (meth) acrylamide. It consists of a water-soluble polymer having a structural unit. First, the monomers necessary for the polymerization constitution will be described.
下記一般式（１）で表される単量体は、（メタ）アクリル酸ジアルキルアミノエチルやジアルキルアミノプロピル（メタ）アクリルアミドなどの塩化ベンジルによる四級化物である。すなわち具体的な例を列記すれば（メタ）アクリロイルオキシエチルベンジルジメチルアンモニウム塩化物、（メタ）アクリロイルオキシ２−ヒドロキシプロピルベンジルジメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルベンジルジメチルアンモニウム塩化物、（メタ）アクリロイルオキシエチルベンジルジエチルアンモニウム塩化物、（メタ）アクリロイルオキシ２−ヒドロキシプロピルベンジルジエチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルベンジルジエチルアンモニウム塩化物などである。
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキル基あるいはアルコキシル基であり、同種でも異種でも良い。Ａ１はＯまたはＮＨ、Ｂ１は炭素数２〜４のアルキレン基、Ｘ１ −は陰イオンをそれぞれ表す。
The monomer represented by the following general formula (1) is a quaternized product of benzyl chloride such as dialkylaminoethyl (meth) acrylate and dialkylaminopropyl (meth) acrylamide. Specifically, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxy 2-hydroxypropylbenzyldimethylammonium chloride, (meth) acryloylaminopropylbenzyldimethylammonium chloride, (meth) ) Acryloyloxyethylbenzyldiethylammonium chloride, (meth) acryloyloxy 2-hydroxypropylbenzyldiethylammonium chloride, (meth) acryloylaminopropylbenzyldiethylammonium chloride, and the like.
R 1 is hydrogen or a methyl group, and R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, which may be the same or different. A 1 is O or NH, B 1 is an alkylene group having 2 to 4 carbon atoms, X 1 - represents each an anion.
下記一般式（２）で表される単量体は、（メタ）アクリル酸ジアルキルアミノエチルやジアルキルアミノプロピル（メタ）アクリルアミドなどの塩化ベンジルによる四級化物である。すなわち具体的な例を列記すれば（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシ２−ヒドロキシプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシエチルトリエチルアンモニウム塩化物、（メタ）アクリロイルオキシ２−ヒドロキシプロピルトリエチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルトリエチルアンモニウム塩化物などである。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、Ｒ７は水素、炭素数１〜３のアルキル基であり、同種でも異種でも良い。Ａ２はＯまたはＮＨ、
Ｂ２は炭素数２〜４のアルキレン基、Ｘ２ −は陰イオンをそれぞれ表す。
The monomer represented by the following general formula (2) is a quaternized product of benzyl chloride such as dialkylaminoethyl (meth) acrylate and dialkylaminopropyl (meth) acrylamide. That is, if specific examples are listed, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy 2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxy Examples thereof include ethyltriethylammonium chloride, (meth) acryloyloxy 2-hydroxypropyltriethylammonium chloride, (meth) acryloylaminopropyltriethylammonium chloride, and the like.
R 4 is hydrogen or a methyl group, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, R 7 is hydrogen and an alkyl group having 1 to 3 carbon atoms, and may be the same or different. A 2 is O or NH,
B 2 represents an alkylene group having 2 to 4 carbon atoms, and X 2 − represents an anion.
水溶性高分子を構成するその他の単量体は、イタコン酸、アクリル酸およびメタアクリル酸のうち一種、アクリルアミドおよびメタアクリルアミドのうち一種である。 The other monomer constituting the water-soluble polymer is one of itaconic acid, acrylic acid and methacrylic acid, and one of acrylamide and methacrylamide.
水溶性高分子を構成する各単量体の共重合比は、使用する製紙薬剤の用途によって適宜決めていく必要がある。すなわち濾水性向上剤あるいは歩留向上剤の場合は、比較的中カチオン量域から低カチオン量域が好ましく、上記一般式（１）で表される単量体が２〜２０モル％、上記一般式（２）で表される単量体が２〜４０モル％、イタコン酸１〜１５モル％、（メタ）アクリル酸１〜１５モル％、（メタ）アクリルアミド１０〜９４モル％の範囲であることが好ましい。さらに好ましくは上記一般式（１）で表される単量体が２〜１０モル％、上記一般式（２）で表される単量体が５〜３０モル％、イタコン酸１〜５モル％、（メタ）アクリル酸１〜１０モル％、（メタ）アクリルアミド４５〜９１モル％の範囲である。これら濾水性向上剤あるいは歩留向上剤の分子量は、重量平均分子量で５００万〜３０００万であり、好ましくは７００万〜３０００万である。 The copolymerization ratio of each monomer constituting the water-soluble polymer needs to be appropriately determined according to the use of the papermaking chemical to be used. That is, in the case of the drainage improver or the yield improver, a relatively medium cation amount range to a low cation amount range are preferable, the monomer represented by the general formula (1) is 2 to 20 mol%, and the general The monomer represented by the formula (2) is in the range of 2 to 40 mol%, itaconic acid 1 to 15 mol%, (meth) acrylic acid 1 to 15 mol%, and (meth) acrylamide 10 to 94 mol%. It is preferable. More preferably, the monomer represented by the general formula (1) is 2 to 10 mol%, the monomer represented by the general formula (2) is 5 to 30 mol%, and itaconic acid is 1 to 5 mol%. , (Meth) acrylic acid 1 to 10 mol%, (meth) acrylamide 45 to 91 mol%. The molecular weight of these drainage improvers or yield improvers is 5 million to 30 million in weight average molecular weight, and preferably 7 million to 30 million.
また層間強度向上剤あるいは紙力増強剤の場合は、比較的低カチオン量域が好ましく、上記一般式（１）で表される単量体２〜１０モル％、上記一般式（２）で表される単量体２〜１０モル％、イタコン酸１〜２０モル％、（メタ）アクリル酸１〜２０モル％、（メタ）アクリルアミド４０〜９４モル％であることが好ましい。またさらに好ましくは上記一般式（１）で表される単量体が２〜５モル％、上記一般式（２）で表される単量体が２〜８モル％、イタコン酸１〜５モル％、（メタ）アクリル酸１〜８モル％、（メタ）アクリルアミド７４〜９４モル％である。これら層間強度向上剤あるいは紙力増強剤の分子量は、重量平均分子量で１５０万〜１０００万であり、好ましくは１５０万〜７００万である。 In the case of an interlayer strength improver or a paper strength enhancer, a relatively low cation amount range is preferred, and the monomer represented by the general formula (1) is represented by 2 to 10 mol%, and represented by the general formula (2). It is preferable that they are 2-10 mol% of monomers, 1-20 mol% of itaconic acid, 1-20 mol% of (meth) acrylic acid, and 40-94 mol% of (meth) acrylamide. More preferably, the monomer represented by the general formula (1) is 2 to 5 mol%, the monomer represented by the general formula (2) is 2 to 8 mol%, and itaconic acid is 1 to 5 mol%. %, (Meth) acrylic acid 1 to 8 mol%, and (meth) acrylamide 74 to 94 mol%. The molecular weight of the interlayer strength improver or paper strength enhancer is 1.5 to 10 million in weight average molecular weight, and preferably 1.5 to 7 million.
更に製紙における欠点発生防止剤の場合は、欠点発生の原因となるアニオントラッシュやピッチ類の性質によってイオン性は、高い領域から低い領域まで様々であり、その結果、上記一般式（１）で表される単量体２〜２０モル％、上記一般式（２）で表される単量体２〜５０モル％、イタコン酸１〜１０モル％、（メタ）アクリル酸１〜１０モル％、（メタ）アクリルアミド１０〜９４モル％である。また更に好ましくは、上記一般式（１）で表される単量体２〜１５モル％、上記一般式（２）で表される単量体２〜５０モル％、イタコン酸１〜８モル％、（メタ）アクリル酸１〜８モル％、（メタ）アクリルアミド１９〜９４モル％である。これら製紙における欠点発生防止剤の分子量は、重量平均分子量で１０万〜１０００万であり、好ましくは２０万〜５００万である。 Further, in the case of a defect-generating inhibitor in papermaking, the ionicity varies from a high region to a low region depending on the properties of anion trash and pitches that cause defects, and as a result, it is represented by the above general formula (1). 2 to 20 mol% of the monomer, 2 to 50 mol% of the monomer represented by the general formula (2), 1 to 10 mol% of itaconic acid, 1 to 10 mol% of (meth) acrylic acid, ( It is 10-94 mol% of (meth) acrylamide. More preferably, the monomer represented by the general formula (1) is 2 to 15 mol%, the monomer represented by the general formula (2) is 2 to 50 mol%, and itaconic acid is 1 to 8 mol%. , (Meth) acrylic acid 1-8 mol%, (meth) acrylamide 19-94 mol%. The molecular weight of the defect-generating inhibitor in these papermaking is 100,000 to 10,000,000, preferably 200,000 to 5,000,000 in terms of weight average molecular weight.
製品形態としては、粉末、油中水型エマルジョン重合物、塩水中分散重合物などのような製品でも使用可能であるが、濾水性向上剤あるいは歩留向上剤の場合は、溶解性や乾燥工程の必要がない油中水型エマルジョン重合物および塩水中分散重合物が最も使用に適している。一方、層間強度向上剤あるいは紙力増強剤の場合は、添加量が比較的高いので水溶液品が適しているが、塩水中分散重合物も好ましく使用可能である。また製紙における欠点発生防止剤の場合は、
油中水型エマルジョン重合物、塩水中分散重合物および水溶液品が使用できる。
As the product form, products such as powder, water-in-oil emulsion polymer, salt-water dispersion polymer, etc. can be used, but in the case of a drainage improver or a yield improver, solubility and drying process Water-in-oil emulsion polymer and salt-in-water dispersion polymer are most suitable for use. On the other hand, in the case of an interlaminar strength improver or a paper strength enhancer, an aqueous solution is suitable because of its relatively high addition amount, but a dispersion polymer in salt water can also be preferably used. In addition, in the case of a defect occurrence preventing agent in papermaking,
Water-in-oil emulsion polymers, salt-in-water dispersion polymers, and aqueous solutions can be used.
塩水溶液中における分散重合物は、カチオン性単量体、アニオン性単量体及び（メタ）アクリルアミドからなる単量体混合物を、塩水溶液中で該塩水溶液に可溶なイオン性高分子からなる分散剤共存下で分散重合法により製造することができる。塩水溶液中で該塩水溶液に可溶なイオン性あるいは非イオン性水溶性高分子からなる分散剤共存下で、攪拌しながら製造された粒径１００μｍ以下の高分子微粒子の分散液を製造する。イオン性高分子からなる分散剤は、例えばアクリロイルオキシエチルトリメチルアンモニウム塩化物の重合体、非イオン性単量体と前記アクリロイルオキシエチルトリメチルアンモニウム塩化物との共重合体などを使用する。非イオン性高分子からなる分散剤は、例えばＮ−ビニルピロリドンの重合体などが使用できる。分子量は重量平均分子量で１万〜２００万程度のものを使用する。 The dispersion polymer in the salt aqueous solution is composed of a monomer mixture composed of a cationic monomer, an anionic monomer and (meth) acrylamide, and an ionic polymer soluble in the salt aqueous solution in the salt aqueous solution. It can be produced by a dispersion polymerization method in the presence of a dispersant. In dispersing agent presence consisting soluble ionic or non-ionic water-soluble polymer in salt solution in an aqueous salt solution, to produce a dispersion of stirring particle size 100 manufactured while μm or less of the polymer particles . As the dispersant made of an ionic polymer, for example, a polymer of acryloyloxyethyltrimethylammonium chloride, a copolymer of a nonionic monomer and the acryloyloxyethyltrimethylammonium chloride, or the like is used. As the dispersant composed of a nonionic polymer, for example, a polymer of N-vinylpyrrolidone can be used. The molecular weight is about 10,000 to 2,000,000 in terms of weight average molecular weight.
塩水溶液を構成する無機塩類は、多価アニオン塩類が、より好ましく、硫酸塩又は燐酸塩が適当であり、具体的には、硫酸アンモニウム、硫酸ナトリウム、硫酸マグネシウム、硫酸アルミニウム、燐酸水素アンモニウム、燐酸水素ナトリウム、燐酸水素カリウム等を例示することができ、これらの塩を濃度１５％以上の水溶液として用いることが好ましい。このなかに前記単量体類を溶解させ、さらにイオン性高分子からなる分散剤を共存させ、ｐＨを２〜５に調製した後、窒素置換後、重合開始剤によって重合を開始させる。 The inorganic salts constituting the aqueous salt solution are more preferably polyvalent anion salts, and sulfates or phosphates are suitable. Specifically, ammonium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, ammonium hydrogen phosphate, hydrogen phosphate Examples thereof include sodium and potassium hydrogen phosphate, and these salts are preferably used as an aqueous solution having a concentration of 15% or more. The monomers are dissolved therein, and a dispersing agent composed of an ionic polymer is allowed to coexist, and the pH is adjusted to 2 to 5. After nitrogen substitution, polymerization is initiated by a polymerization initiator.
重合濃度としては、単量体濃度として１５重量％〜３５重量％であるが、好ましくは２０重量％〜３０重量％である。単量体供給方法としては、重合開始持、一括でも良いし、適宜分割して供給しても良い。 The polymerization concentration is 15% to 35% by weight as the monomer concentration, but preferably 20% to 30% by weight. As the monomer supply method, polymerization may be started or batched, or may be divided and supplied as appropriate.
油中水型エマルジョン重合法は、単量体あるいは共重合可能な二種以上の単量体からなる単量体混合物を水、少なくとも水と非混和性の炭化水素からなる油状物質、油中水型エマルジョンを形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤を混合し、強攪拌し油中水型分散液を形成させた後、重合することにより合成する方法である。 The water-in-oil emulsion polymerization method comprises a monomer or a monomer mixture composed of two or more types of copolymerizable monomers, water, an oily substance composed of at least water-immiscible hydrocarbons, water-in-oil. This is a method of synthesizing by mixing an effective amount for forming a mold emulsion and at least one surfactant having HLB, and stirring strongly to form a water-in-oil dispersion, followed by polymerization.
分散媒として使用する炭化水素からなる油状物質の例としては、パラフィン類あるいは灯油、軽油、中油などの鉱油、あるいはこれらと実質的に同じ範囲の沸点や粘度などの特性を有する炭化水素系合成油、あるいはこれらの混合物があげられる。含有量としては、油中水型分散液全量に対して２０質量％〜５０質量％の範囲であり、好ましくは２０質量％〜４０質量％の範囲である。 Examples of oily substances composed of hydrocarbons used as a dispersion medium include paraffins, mineral oils such as kerosene, light oil, and middle oil, or hydrocarbon-based synthetic oils having characteristics such as boiling point and viscosity in substantially the same range as these. Or a mixture thereof. As content, it is the range of 20 mass%-50 mass% with respect to the water-in-oil type dispersion liquid whole quantity, Preferably it is the range of 20 mass%-40 mass%.
油中水型分散液を形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤の例としては、ＨＬＢ３〜１３のノニオン性界面活性剤であり、その具体例としては、油溶性界面活性剤のソルビタンモノオレ−ト、ソルビタンモノステアレ−ト、ソルビタンモノパルミテ−トなどがあげられる。またノニオン性水溶性界面活性剤としては、ポリオキシエチレンアルキルエ−テル系、ポリオキシエチレンアルコールエ−テル系、ポリオキシエチレンアルキルエステル系などである。具体的には、ポリオキシエチレン（２０）ソルビタントリオレート、ポリオキシエチレン（４）ソルビタンモノステアレート、ポリオキシエチレン（５）ソルビタンモノオレートなどである。これら界面活性剤の添加量としては、油中水型エマルジョン全量に対して０．５〜１０質量％であり、好ましくは１〜５質量％の範囲である。 Examples of at least one surfactant having an amount effective to form a water-in-oil dispersion and HLB are HLB 3 to 13 nonionic surfactants, specific examples of which are oil-soluble interfaces. Examples of the activator include sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate and the like. Nonionic water-soluble surfactants include polyoxyethylene alkyl ether, polyoxyethylene alcohol ether, and polyoxyethylene alkyl ester. Specifically, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (5) sorbitan monooleate and the like. The addition amount of these surfactants is 0.5 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the water-in-oil emulsion.
重合後は、転相剤と呼ばれる親水性界面化成剤を添加して油の膜で被われた分散粒子が水になじみ易くし、中の水溶性高分子が溶解しやすくする処理を必要に応じて行い、水で希釈しそれぞれの用途に用いる。親水性界面化成剤の例としては、カチオン性界面化成剤やＨＬＢ９〜１５のノニオン性界面化成剤であり、ポリオキシエチレンポリオキシプロピレンアルキルエ−テル系、ポリオキシエチレンアルコールエ−テル系などである。 After the polymerization, a hydrophilic interfacial modifier called a phase inversion agent is added to make the dispersed particles covered with the oil film easy to adjust to water, and the water-soluble polymer inside is easily dissolved as necessary. Dilute with water and use for each application. Examples of hydrophilic interfacial chemicals are cationic interfacial chemicals and nonionic interfacial chemicals of HLB 9-15, such as polyoxyethylene polyoxypropylene alkyl ether systems and polyoxyethylene alcohol ether systems. is there.
本発明の水溶性高分子を層間強度向上剤あるいは紙力増強剤として使用することができる。今日のように資源の節約、リサイクル意識の高まりにより紙・板紙のリサイクルの比率が増加し、古紙が製紙原料へ多量に混入してきている状況下においても、従来の単なる古紙新聞紙が混入するだけでなく、チラシ類が選別されることなく混入する。チラシ類は、塗工紙である場合がほぼ全てであり、それに伴い炭酸カルシウム、顔料、糊料、ラテクッス類などが一緒に入り、更に古紙配合率増加に伴う用水悪化などは、ワイヤー上の歩留率および紙質低下の方向に作用することは避けられない。このような製紙状況においても優れた紙力増強効果や層間強度向上を発揮することが可能である。製紙原料の乾燥固形分に対する添加量は、０．１〜０．５質量％程度添加するのが目安となる。製紙原料の種類としては、層間強度向上の場合はライナ−、中芯原紙、白ボールなど板紙の他、洋紙にも適用できる。抄紙ｐＨは、酸性からアルカリ性の３〜１０でも単量体組成、あるいは分子量を調節することで対応することが可能である。 The water-soluble polymer of the present invention can be used as an interlayer strength improver or paper strength enhancer. Even in today's situation where the recycling ratio of paper and paperboard has increased due to resource conservation and increased awareness of recycling, even in the situation where a large amount of used paper is mixed into the raw material for papermaking, conventional wastepaper newspaper can be mixed in There is no mixing of leaflets without sorting. Flyers are almost all coated papers, and calcium carbonate, pigments, glues, latexes, etc. are included together with it, and the deterioration of water usage due to an increase in the ratio of used paper is a step on the wire. It is unavoidable to act in the direction of the yield and paper quality. Even in such a papermaking situation, it is possible to exhibit an excellent paper strength enhancing effect and interlayer strength improvement. As a guideline, the amount of the papermaking raw material to be added to the dry solid content is about 0.1 to 0.5% by mass. As the type of papermaking raw material, in the case of improving the interlayer strength, it can be applied not only to paperboard such as liner, core raw paper, and white ball, but also to paper. The papermaking pH can be adjusted from acidic to alkaline 3 to 10 by adjusting the monomer composition or molecular weight.
製紙における欠点防止処理は、以下のように処理することが可能である。すなわち古紙の配合率の高まりによって、アニオントラッシュと呼ばれる溶存性あるいは親水性のアニオン性成分、すなわちホワイト顔料、分散剤、改質でんぷん、カルボキシメチルセルロース、リグニンスルホネート、リグニン分解生成物、ヘミセルロースなどの混入量が増加しているが、これらは低分子量カチオン性水溶性高分子物質により処理することによって歩留率や濾水性はかなりの程度改善される。これらに対応させるためには、本発明の水溶性高分子の分子量を１万〜１００万程度にし、イオン量は上記一般式（１）あるいは上記一般式（２）で表わされる単量体の共重合率を高く設定することにより、顕著な効果を発揮するものを合成することができる。また水に溶解しない疎水的な成分ピッチあるいはスティッキーは、上記一般式（１）で表わされる単量体の共重合率を調節し、イオン量も低めに設定することにより対応させることが可能である。製紙原料の乾燥固形分に対する添加量は、０．０５〜０．２質量％程度添加するのが目安となる。製紙工程における添加場所は、古紙やその他のパルプを配合する原料チェストや配合チェストの配管入り口や出口が最適であるが、他の製紙薬剤が添加されるマシンチェストや種箱でも効果がある。 The defect prevention process in papermaking can be performed as follows. In other words, due to an increase in the ratio of used paper, the amount of dissolved or hydrophilic anionic components called anionic trash, that is, white pigment, dispersant, modified starch, carboxymethylcellulose, lignin sulfonate, lignin degradation products, hemicellulose, etc. However, when these are treated with a low molecular weight cationic water-soluble polymer substance, the yield and drainage are improved to a considerable extent. In order to cope with these, the molecular weight of the water-soluble polymer of the present invention is set to about 10,000 to 1,000,000, and the ion amount is the same as that of the monomer represented by the general formula (1) or the general formula (2). By setting the polymerization rate high, it is possible to synthesize one that exhibits a remarkable effect. Further, the hydrophobic component pitch or sticky that does not dissolve in water can be dealt with by adjusting the copolymerization rate of the monomer represented by the general formula (1) and setting the ion amount lower. . As a guideline, the amount of the papermaking raw material to be added to the dry solid content is about 0.05 to 0.2% by mass. The addition place in the papermaking process is optimal at the raw material chest for mixing waste paper and other pulp and the piping entrance and exit of the blended chest, but it is also effective in machine chests and seed boxes to which other papermaking chemicals are added.
上記のように近年においては資源の節約、リサイクル意識の高まりにより紙・板紙のリサイクルの比率が増加し、古紙が製紙原料へ多量に混入してきている。
新聞用紙においては、従来の単なる古紙新聞紙が混入するだけでなく、チラシ類が選別されることなく混入する。チラシ類は、塗工紙である場合がほぼ全てであり、それに伴い炭酸カルシウム、顔料、糊料、ラテクッス類などが一緒に入り、更に古紙配合率増加に伴う用水悪化などは、ワイヤー上の歩留率および紙質低下の方向に作用することは避けられない。本発明の水溶性高分子によって、このような製紙原料および製紙用水の悪化にも対応できる層間強度向上剤あるいは紙力増強剤を製造することができる。そのため既存のジメチルアミノエチルメタアクリレート三級塩、アクリル酸とアクリルアミドの共重合物に替わり、ジメチルアミノエチルアクリレート四級塩、ジメチルアミノエチルアクリレートのベンジルクロライド四級化物、アクリル酸、イタコン酸、アクリルアミドの共重合物の特別なイオン的効果によって古紙の配合率の増加や、アニオントラッシュなど薬剤の定着に妨げとなる不純物の存在下でも高い紙力増強を発現する製紙薬剤が製造可能である。
As described above, in recent years, the ratio of paper and paperboard recycling has increased due to resource conservation and increased awareness of recycling, and a large amount of used paper has been mixed into papermaking raw materials.
In newspaper paper, not only conventional mere waste paper but also leaflets are mixed without being sorted. Flyers are almost all coated papers, and calcium carbonate, pigments, glues, latexes, etc. are included together with it, and the deterioration of water usage due to an increase in the ratio of used paper is a step on the wire. It is unavoidable to act in the direction of the yield and paper quality. The water-soluble polymer of the present invention makes it possible to produce an interlayer strength improver or paper strength enhancer that can cope with such deterioration of papermaking raw materials and papermaking water. Therefore, instead of existing dimethylaminoethyl methacrylate tertiary salt and acrylic acid and acrylamide copolymer, dimethylaminoethyl acrylate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternized product, acrylic acid, itaconic acid, acrylamide It is possible to produce a papermaking agent that exhibits a high paper strength enhancement even in the presence of impurities such as an increase in the ratio of used paper due to the special ionic effect of the copolymer and an impediment to fixing of the agent such as anion trash.
本発明の水溶性高分子からなる製紙用薬剤の適用される紙製品としては、一般の印刷用紙、包装用紙、ダンボ−ル用ライナ−や中芯原紙などいずれでも使用可能である。また抄紙ｐＨとしては、３〜９など酸性から中性・アルカリ抄紙である。 As a paper product to which the paper-making chemical comprising the water-soluble polymer of the present invention is applied, any of general printing paper, packaging paper, cardboard liner, core base paper, and the like can be used. The papermaking pH is from acidic to neutral / alkali papermaking such as 3-9.
（実施例） 以下、実施例および比較例によって本発明をさらに詳しく説明するが、本発明はその要旨を超えない限り、以下の実施例に制約されるものではない。 (Examples) Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist.
（合成例１）攪拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１１５ｇにポリオキシエチレン（２０）ソルビタントリオレート１０．０ｇを仕込み溶解させた。別にアクリロイルオキシエチルトリメチルアンモニウム塩化物（以下ＤＭＱと略記）８０％水溶液８２．２ｇ、アクリロイルオキシエチルベンジルジメチルアンモニウム塩化物８０％水溶液（以下ＤＭＢＣと略記）５２．８ｇ、イタコン酸（ＩＡと略記）６．７ｇ、アクリル酸６．１ｇ（ＡＡＣと略記）、アクリルアミド（ＡＡＭと略記）５０％水溶液１４９．６ｇ、およびイオン交換水６７．６ｇを各々混合し完全に溶解させた。その後油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで１５分間攪拌乳化した。この時の単量体組成は、ＤＭＱ／ＤＭＢＣ／ＩＡ／ＡＡＣ／ＡＡＭ＝２０／１０／３／５／６２（モル％）である。得られたエマルジョンを単量体溶液の温度を４０〜４３℃に保ち、窒素置換を３０分行なった後、ジメチル−２，２−アゾビスイソブチレート（和光純薬製Ｖ−６０１）０．０２ｇ（対単量体０．０１質量％）を加え、重合反応を開始させた。反応温度を４２±２℃で１２時間重合させ反応を完結させた。その後、転相剤としてポリオキシエチレン（２０）ソルビタントリオレート１０ｇ（液総量に対し１０質量％となるように添加）を添加した。転相剤添加後の油中水型エマルジョン粘度は、２８０ｍＰａ・ｓであり、動的光散乱法による重量平均分子量は、１８００万であった。これを試料−１とする。同様な操作によって表１に記載する組成により試料−２〜試料−３を合成した。結果を表１に示す。 (Synthesis Example 1) 10.0 g of polyoxyethylene (20) sorbitan trioleate was charged and dissolved in 115 g of isoparaffin having a boiling point of 190 ° C to 230 ° C in a reaction vessel equipped with a stirrer and a temperature controller. Separately, 82.2 g of 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride (hereinafter abbreviated as DMQ), 52.8 g of 80% aqueous solution of acryloyloxyethylbenzyldimethylammonium chloride (hereinafter abbreviated as DMBC), and itaconic acid (abbreviated as IA) 6 0.7 g, acrylic acid 6.1 g (abbreviated as AAC), acrylamide (abbreviated as AAM) 50% aqueous solution 149.6 g, and ion-exchanged water 67.6 g were mixed and dissolved completely. Thereafter, the oil and the aqueous solution were mixed, and stirred and emulsified with a homogenizer at 1000 rpm for 15 minutes. The monomer composition at this time is DMQ / DMBC / IA / AAC / AAM = 20/10/3/5/62 (mol%). The obtained emulsion was maintained at a temperature of the monomer solution at 40 to 43 ° C. and purged with nitrogen for 30 minutes, and then dimethyl-2,2-azobisisobutyrate (V-601, manufactured by Wako Pure Chemical Industries). 02 g (0.01% by mass of monomer) was added to initiate the polymerization reaction. The reaction was completed at a reaction temperature of 42 ± 2 ° C. for 12 hours to complete the reaction. Thereafter, 10 g of polyoxyethylene (20) sorbitan trioleate (added so as to be 10% by mass with respect to the total amount of the liquid) was added as a phase inversion agent. The water-in-oil emulsion viscosity after the addition of the phase inversion agent was 280 mPa · s, and the weight average molecular weight determined by the dynamic light scattering method was 18 million. This is designated as Sample-1. Sample-2 to sample-3 were synthesized by the same procedure as described in Table 1. The results are shown in Table 1.
（合成例２）重合時にメチレンビスアクリルアミド０．１％水溶液０．４ｇ（対単量体０．０００２質量％）およびイソプロピルアルコール０．１ｇ（対単量体０．０５質量％）を添加した他は試料−１と同様な操作により試料−４を合成した。結果を表１に示す。 (Synthesis Example 2) In addition to the polymerization, 0.4 g of methylenebisacrylamide 0.1% aqueous solution (0.0002% by mass with respect to monomer) and 0.1 g of isopropyl alcohol (0.05% by mass with respect to monomer) were added. Sample 4 was synthesized by the same operation as sample-1. The results are shown in Table 1.
（合成例３）
アクリロイルオキシエチルトリメチルアンモニウム塩化物８０％水溶液１０．３ｇ、アクリロイルオキシエチルベンジルジメチルアンモニウム塩化物８０％水溶液６．６ｇ、イタコン酸１．９ｇ、アクリル酸２．０ｇ、アクリルアミド５０％水溶液８５．６ｇおよびイオン交換水１９０ｇを各々混合し、完全に溶解させ単量体として２０質量％水溶液を調製した。この時の単量体組成は、ＤＭＱ／ＤＭＢＣ／ＩＡ／ＡＡＣ／ＡＡＭ＝６／３／２／４／８５（モル％）である。これにイソプロピルアルコール０．０９ｇ（対単量体０．１５質量％）を添加し、４０℃一定で２，２−アゾビスアミジノプロパン２塩化水素化物を開始剤として水溶液重合品試料−５を合成した。水溶液粘度は８１００ｍＰａ・ｓであり、動的光散乱法による重量平均分子量は、２５０万であった。結果を表１に示す。
(Synthesis Example 3)
Acryloyloxyethyltrimethylammonium chloride 80% aqueous solution 10.3 g, acryloyloxyethylbenzyldimethylammonium chloride 80% aqueous solution 6.6 g, itaconic acid 1.9 g, acrylic acid 2.0 g, acrylamide 50% aqueous solution 85.6 g and ions Each exchange water 190g was mixed, and it melt | dissolved completely, and prepared 20 mass% aqueous solution as a monomer. The monomer composition at this time is DMQ / DMBC / IA / AAC / AAM = 6/3/2/4/85 (mol%). To this was added 0.09 g of isopropyl alcohol (0.15% by mass relative to the monomer), and an aqueous solution polymer sample-5 was synthesized using 2,2-azobisamidinopropane dihydrochloride as an initiator at a constant 40 ° C. did. The aqueous solution viscosity was 8100 mPa · s, and the weight average molecular weight determined by the dynamic light scattering method was 2.5 million. The results are shown in Table 1.
（合成例４）
合成例３と同様な操作により表１に記載する組成により試料−６〜試料−１０を合成した。結果を表１に示す。
(Synthesis Example 4)
Sample-6 to Sample-10 were synthesized according to the composition described in Table 1 by the same operation as in Synthesis Example 3. The results are shown in Table 1.
（合成例５）攪拌機、還流冷却管、温度計および窒素導入管を備えた４つ口５００ｍｌセパラブルフラスコに脱イオン水：７３．３ｇ、アクリロイルオキシエチルトリメチルアンモニウム塩化物８０％水溶液５．３ｇ、アクリロイルオキシエチルベンジルジメチルアンモニウム塩化物８０％水溶液４．６ｇ、イタコン酸４．８ｇ、アクリル酸５．３ｇ、アクリルアミド５０％水溶液８４．０ｇ、硫酸アンモニウム７５ｇ、分散剤として２０質量％水溶液のアクリルアミド２-メチルプロパンスルホン酸重合体（分子量：２０万、２０当量％中和物）２４．０ｇ（対単量体８．０質量％）を各々混合し、完全に溶解させた。この時の単量体組成は、ＤＭＱ／ＤＭＢＣ／ＩＡ／ＡＡＣ／ＡＡＭ＝３／２／５／１０／８０（モル％）である。その後、攪拌しながら窒素導入管より窒素を導入し溶存酸素の除去を行う。この間恒温水槽により２５℃に内部温度を調整する。窒素導入３０分後、０．２質量％のペルオキソニ硫酸アンモニウム及び亜硫酸水素アンモニウムの０．２質量％水溶液をそれぞれこの順で２．５ｇ（対単量体、４０ｐｐｍ）添加し重合を開始させた。開始剤添加２時間後、反応物液の粘性が、やや上昇したがそれ以上増加せず、重合開始後８時間たったところで前記開始剤をそれぞれ同量追加し、さらに１５時間重合を継続させ反応を終了した。この試作品を試料−１１とする。この試料−１１の粘度は２７０ｍＰａ・ｓであり、動的光散乱法による重量平均分子量は、２４０万であった。
なお、顕微鏡観察の結果、２〜２０μｍの粒子であることが判明した。組成を表１に示す。
(Synthesis Example 5) In a 4-neck 500 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, deionized water: 73.3 g, acryloyloxyethyltrimethylammonium chloride 80% aqueous solution 5.3 g, Acryloyloxyethylbenzyldimethylammonium chloride 80% aqueous solution 4.6 g, Itaconic acid 4.8 g, Acrylic acid 5.3 g, Acrylamide 50% aqueous solution 84.0 g, Ammonium sulfate 75 g, 20% by weight aqueous solution acrylamide 2-methyl Propanesulfonic acid polymer (molecular weight: 200,000, 20 equivalent% neutralized product) of 24.0 g (8.0% by mass of monomer) was mixed and dissolved completely. The monomer composition at this time is DMQ / DMBC / IA / AAC / AAM = 3/2/5/10/80 (mol%). Thereafter, nitrogen is introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature is adjusted to 25 ° C. using a constant temperature water bath. 30 minutes after the introduction of nitrogen, 2.5 g (0.2% by mass, 40 ppm) of 0.2% by mass ammonium peroxodisulfate and 0.2% by mass aqueous solution of ammonium hydrogen sulfite were added in this order to initiate the polymerization. 2 hours after the addition of the initiator, the viscosity of the reaction liquid slightly increased but did not increase any more. After 8 hours from the start of polymerization, the same amount of the initiator was added, and the polymerization was continued for another 15 hours. finished. This prototype is designated as Sample-11. The viscosity of Sample-11 was 270 mPa · s, and the weight average molecular weight determined by the dynamic light scattering method was 2.4 million.
Microscopic observation revealed that the particles were 2 to 20 μm. The composition is shown in Table 1.
（合成例６）合成例５と同様な操作で試料−１２〜試料−１４を合成した。組成を表１に示す。 (Synthesis Example 6) Samples 12 to 14 were synthesized in the same manner as in Synthesis Example 5. The composition is shown in Table 1.
（表１）
各単量体組成はモル％、ＭＢＡ；メチレンビスアクリルアミドは、単量体総量に対する質量％、反応物粘度；ｍＰａ・ｓ、分子量；単位は万、形態；ＥＭ：油中水型エマルジョン、ＡＱ：水溶液、ＤＩ：塩水中分散液
(Table 1)
Each monomer composition is mol%, MBA; methylenebisacrylamide is mass% with respect to the total amount of monomers, reactant viscosity; mPa · s, molecular weight; unit is 10,000, form; EM: water-in-oil emulsion, AQ: Aqueous solution, DI: dispersion in brine
新聞用紙製造用の製紙原料（ｐＨ７．６８、全ＳＳ分４．５２質量％、灰分０．３０質量％）を用い、パルプ濃度０．８質量％に水道水を用いて希釈、ブリット式ダイナミックジャ−テスタ−により歩留率を測定した。添加薬品として、炭酸カルシウム対製紙原料８質量％（以下同様）、本発明の高分子量水溶性重合体を含有する分散液（試料−１〜試料−４）０．０３質量％をそれぞれこの順に１５秒間隔で添加し、攪拌を開始する。製紙原料の薬剤添加後のｐＨは、８．０２であった。３０秒後に１０秒間白水を排出し、３０秒間白水を採取し、下記条件で総歩留率を測定した。攪拌条件は、回転数１２００ｒｐｍ、ワイヤー１２５Ｐスクリーン（２００メッシュ相当）、総歩留率（ＳＳ濃度）はＡＤＶＡＮＴＥＣ ＮＯ．２にて濾過し測定した。また乾燥後、濾紙を５２５℃で焼却し灰分を測定し、歩留率を算出した。測定結果を表２に示す。 Using a papermaking raw material (pH 7.68, total SS content 4.52% by mass, ash content 0.30% by mass) for newsprint production, diluted with tap water to a pulp concentration of 0.8% by mass, a britt dynamic jar -Yield rate was measured with a tester. As additive chemicals, calcium carbonate vs. 8% by mass of papermaking raw material (hereinafter the same), and 0.03% by mass of the dispersion (sample-1 to sample-4) containing the high-molecular-weight water-soluble polymer of the present invention are each 15 in this order. Add in seconds and start stirring. The pH of the papermaking raw material after addition of the drug was 8.02. After 30 seconds, white water was discharged for 10 seconds, white water was collected for 30 seconds, and the total yield was measured under the following conditions. The stirring conditions were 1200 rpm, wire 125P screen (equivalent to 200 mesh), and the total yield (SS concentration) was ADVANTEC NO. It filtered and measured by 2. After drying, the filter paper was incinerated at 525 ° C., the ash content was measured, and the yield was calculated. The measurement results are shown in Table 2.
（比較試験１）同様な試験を比較−１〜比較−３に関し実施した。結果を表２に示す。 (Comparative Test 1) A similar test was performed for Comparative-1 to Comparative-3. The results are shown in Table 2.
（表２）
添加量；対製紙原料（％）、総歩留率；質量％、灰分歩留率；質量％
(Table 2)
Amount of addition: raw material for papermaking (%), total yield: mass%, ash yield: mass%
上質紙製造用の製紙原料（ｐＨ６．０９、全ＳＳ分３．５質量％、灰分０．４５質量％）を用いてパルプ濃度０．８質量％に水道水を用いて希釈、ブリット式ダイナミックジャ−テスタ−により歩留率を測定した。添加薬品として、両性変性デンプン対製紙原料０．５質量％（以下同様）、炭酸カルシウム３０質量％、中性ロジンサイズ０．２０質量％、硫酸バンド１．０質量％、本発明の両性水溶性高分子（試料−１〜試料−４）０．０２質量％、製紙用ベントナイト０．１質量％、あるいはアニオン性水溶性高分子（試料−１４）０．０２質量％をそれぞれこの順に１５秒間隔で添加し、攪拌を開始する。薬剤添加後の製紙原料ｐＨは、７．０２であった。３０秒後に１０秒間白水を排出し、３０秒間白水を採取し、下記条件で総歩留率を測定した。攪拌条件は、回転数１２００ｒｐｍ、ワイヤー１２５Ｐスクリーン（２００メッシュ相当）、総歩留率（ＳＳ濃度）はＡＤＶＡＮＴＥＣ ＮＯ．２にて濾過し測定した。また乾燥後、濾紙を５２５℃で焼却し灰分を測定し、歩留率を算出した。測定結果を表３に示す。 Diluted with tap water to a pulp concentration of 0.8% by weight using papermaking raw materials (pH 6.09, total SS content 3.5% by weight, ash content 0.45% by weight) for producing fine paper, Brit-type dynamic jar -Yield rate was measured with a tester. As additive chemicals, amphoteric modified starch to paper raw material 0.5% by mass (hereinafter the same), calcium carbonate 30% by mass, neutral rosin size 0.20% by mass, sulfuric acid band 1.0% by mass, amphoteric water-soluble of the present invention Polymer (sample-1 to sample-4) 0.02% by mass, papermaking bentonite 0.1% by mass, or anionic water-soluble polymer (sample-14) 0.02% by mass in this order at intervals of 15 seconds And start stirring. The papermaking raw material pH after the chemical addition was 7.02. After 30 seconds, white water was discharged for 10 seconds, white water was collected for 30 seconds, and the total yield was measured under the following conditions. The stirring conditions were 1200 rpm, wire 125P screen (equivalent to 200 mesh), and the total yield (SS concentration) was ADVANTEC NO. It filtered and measured by 2. After drying, the filter paper was incinerated at 525 ° C., the ash content was measured, and the yield was calculated. Table 3 shows the measurement results.
（比較試験２）同様な試験を比較−１〜比較−３に関し実施した。結果を表３に示す。
(Comparative Test 2) A similar test was performed for Comparative-1 to Comparative-3. The results are shown in Table 3.
（表３）
添加量；対製紙原料（％）、総歩留率；質量％、灰分歩留率；質量％
ＢＴ；ベントナイト、ＡＰ；
(Table 3)
Amount of addition: raw material for papermaking (%), total yield: mass%, ash yield: mass%
BT; bentonite, AP;
ダンボ−ルのライナー用原料（ｐＨ５．５０、全ｓｓ３．８％、灰分０．１８％）を用い、パルプ濃度０．７重量％に水道水を用いて希釈した。この製紙原料を用い１００ｇ／ｍ２の紙を抄いた。添加薬品として、ロジンサイズ０．１５％（対乾燥パルプ、以下同様）、硫酸バンド２．５％、紙力増強剤として表１の試料−５〜試料−７、０．２５％、および歩留向上剤としてポリアクリルアミド系高分子凝集剤（カチオン性アクリルエステル系共重合物、重量平均分子量１５００万）０．０１５％をそれぞれこの順で、攪拌機により３００ｒｐｍで攪拌しながら１５秒間隔により添加した後、タッピスタンダ−ド抄紙機により抄紙した。薬品添加後の製紙原料ｐＨは、４．３３であった。得られた湿紙を３．５Ｋｇ／ｍ２で５分間プレスし、１００℃で２分間乾燥した。その後、２０℃、６５ＲＨの条件で調湿し、引っ張り強度を測定後、裂断長を算出し（ＪＩＳ−Ｐ８１１３）、また灰分含有率（８００℃、１時間強熱残さ）を測定した。結果を表４に示す。 The material for the liner of the liner (pH 5.50, total ss 3.8%, ash content 0.18%) was used and diluted with tap water to a pulp concentration of 0.7% by weight. Using this papermaking raw material, paper of 100 g / m 2 was made. As additive chemicals, rosin size 0.15% (vs dry pulp, the same applies below), sulfuric acid band 2.5%, paper strength enhancers Sample-5 to Sample-7 in Table 1, 0.25%, and yield After adding 0.015% of polyacrylamide polymer flocculant (cationic acrylic ester copolymer, weight average molecular weight of 15 million) as an improver in this order at intervals of 15 seconds while stirring with a stirrer at 300 rpm. Paper was made with a tappi standard paper machine. The papermaking raw material pH after the chemical addition was 4.33. The obtained wet paper was pressed at 3.5 kg / m 2 for 5 minutes and dried at 100 ° C. for 2 minutes. Thereafter, the humidity was adjusted under the conditions of 20 ° C. and 65 RH, the tensile strength was measured, the tear length was calculated (JIS-P8113), and the ash content (800 ° C., 1 hour ignition residue) was measured. The results are shown in Table 4.
（比較試験３）同様な試験を比較−６（市販両性紙力増強剤；ポリアクリルアミド系、カチオン化度；６モル％、アニオン化度８モル％、重量平均分子量１５０万）、比較−７（アクリルアミド、メタクリル酸ジメチルアミノエチル、アクリル酸共重合物の組成がそれぞれ８６モル％、９モル％、５モル％、重量平均分子量２００万）に関し同様な操作によって実施した。結果を表４に示す。 (Comparative Test 3) Comparative test 6 (commercial amphoteric paper strength enhancer; polyacrylamide, cationization degree: 6 mol%, anionization degree 8 mol%, weight average molecular weight 1,500,000), comparison-7 ( The composition of acrylamide, dimethylaminoethyl methacrylate, and acrylic acid copolymer was 86 mol%, 9 mol%, 5 mol%, and the weight average molecular weight was 2 million, respectively. The results are shown in Table 4.
（表４）
紙中灰分（％）、サイズ度（ステキヒスト、秒）、裂断長（Ｋｍ）
(Table 4)
Ash content in paper (%), sizing degree (stickiness, seconds), tearing length (Km)
ダンボール古紙をパルパーにより離解後、ナイヤガラ式ビ−タ−にて叩解し、カナディアンスタンダ−ドフリーネスＣ．Ｆ．Ｓ＝４００ｍｌに調整した。この分散液に液体硫酸バンド２．５％添加しｐＨを４．３に調節した。その後、市販の両性紙力増強剤（ポリアクリルアミド系、カチオン化度；６モル％、アニオン化度８モル％、重量平均分子量１５０万）を対パルプ０．１５％添加して攪拌し均一に混合した。得られたパルプスラリ−を０．５％に希釈し、抄紙ｐＨを測定した後、タッピスタンダ−ドシ−トマシン（１／１６ｍ２）に１Ｌ入れ乾燥坪量８０ｇ／ｍ２の紙を抄紙した。ワイヤ−上のウェットシ−トに濾紙、ク−チプレ−トを乗せク−チロ−ル３回かけ湿紙を濾紙に転写した。これをＡ層とした。次いで同様に乾燥坪量８０ｇ／ｍ２の紙を抄紙し、ワイヤ−にのせたまま湿紙を直示天秤にて、試作−１１〜試作−１３を表５に記載した所定の希釈濃度に希釈した分散液を圧力２．５気圧で１０．０ｇノズルよりスプレ−塗布した。これをＢ層とした。 After disassembling the corrugated cardboard with a pulper, beat it with a Niagara type beater, Canadian Standard Freeness C.I. F. Adjusted to S = 400 ml. To this dispersion, 2.5% liquid sulfuric acid band was added to adjust the pH to 4.3. Thereafter, 0.15% of a commercially available amphoteric paper strength enhancer (polyacrylamide, cationization degree: 6 mol%, anionization degree 8 mol%, weight average molecular weight 1,500,000) with respect to pulp was added and stirred to mix uniformly. did. The obtained pulp slurry was diluted to 0.5%, and the papermaking pH was measured. Then, 1 L was put into a tap stand standard dough machine (1/16 m 2 ), and paper with a dry basis weight of 80 g / m 2 was made. A filter paper and a cup plate were placed on the wet sheet on the wire, and the wet paper was transferred to the filter paper by applying the cupty roll three times. This was designated as A layer. Then, similarly, paper having a dry basis weight of 80 g / m 2 is made, and the wet paper is put on the wire and the wet paper is diluted with the direct balance to make the prototypes 11 to 13 to the predetermined dilution concentrations described in Table 5. The resulting dispersion was spray coated from a 10.0 g nozzle at a pressure of 2.5 atmospheres. This was designated as layer B.
Ａ層を濾紙がついたままＢ層に合わせ、その後濾紙を剥がした。これをワイヤ−ごとシ−トマシンに戻し、シ−トマシンに水を張りワイヤ−の下まで満たした水を排水することにより減圧脱水し、新たに濾紙を乗せ、ク−チロ−ルを３回かけ濾紙に転写させた。転写した湿紙を２枚の濾紙に挟み、３ｋｇ／ｍ２の圧力で５分間プレス後、ロ−タリ−ドライヤ−で乾燥させて抄き合わせ紙をえた。得られた抄き合わせ紙を調湿後Ｊ−ＴＡＰＰＩ紙パルプ試験法ＮＯ．１９−７７に従って、Ｔ字剥離強さ（ｇｆ／５ｃｍ）を測定した。結果を表５に示す。 The A layer was combined with the B layer with the filter paper attached, and then the filter paper was peeled off. Return this to the sheet machine together with the wire, fill the sheet machine with water, drain the water filled to the bottom of the wire, dewater it under reduced pressure, place a new filter paper, and apply the cupolol three times. Transfered to filter paper. The transferred wet paper was sandwiched between two filter papers, pressed at a pressure of 3 kg / m 2 for 5 minutes, and then dried with a rotary dryer to obtain a laminated paper. After the humidity control of the obtained laminated paper, J-TAPPI paper pulp test method NO. T-peel strength (gf / 5 cm) was measured according to 19-77. The results are shown in Table 5.
（比較試験４）
実施例４と同様な操作によって、比較−４（表１の塩水中分散重合物）、比較−８（水溶液重合物；アクリルアミド、メタクリル酸ジメチルアミノエチル、アクリル酸共重合物の組成がそれぞれ８６モル％、９モル％、５モル％、重量平均分子量２００万）比較−９（馬鈴薯澱粉）につき試験した。結果を表５に示す。
(Comparative test 4)
By the same operation as in Example 4, Comparative-4 (dispersed polymer in salt water of Table 1) and Comparative-8 (aqueous solution polymer; acrylamide, dimethylaminoethyl methacrylate, acrylic acid copolymer each had a composition of 86 mol. %, 9 mol%, 5 mol%, weight average molecular weight 2 million) Comparative-9 (potato starch) was tested. The results are shown in Table 5.
（表５）
塗布濃度：質量％、塗布量：ｇ／ｍ２、Ｔ字剥離強さ：（ｇｆ／５ｃｍ）
(Table 5)
Coating concentration: mass%, coating amount: g / m 2 , T-shaped peel strength: (gf / 5 cm)
ライナー原紙用製紙原料（ｐＨ６．５２、ワットマン濾紙Ｎｏ．４１による濾過後の乾燥固形分３．６６質量％）を用い、製紙における欠点発生防止剤の試験を行った。すなわち前記表１の水溶性高分子試料―８〜試料―１０を乾燥製紙原料当たり０．０３質量％添加し６０秒攪拌した後、製紙現場より採取した白水（ｐＨ５．３０、乾燥固形分０．２１質量％）により希釈し（希釈後の濃度１．０質量％）６０秒間攪拌した。その後ワットマン濾紙Ｎｏ．４１により濾過し、濾液の濁度をＨＡＣＨ社製２１００Ｐ型により、アニオントラッシュのカチオン要求量をＢＴＧ社製ＰＣＤ−０３型により測定した。
Using a papermaking raw material for liner base paper (pH 6.52, dry solid content of 3.66% by mass after filtration with Whatman filter paper No. 41), a test for a defect generation inhibitor in papermaking was performed. That after a water-soluble polymer samples -8 sample -10 before Symbol Table 1 and stirred dry paper stock per 0.03 wt% added 60 seconds, white water (PH5.30 collected from papermaking field, dry solids 0 .21 mass%) (concentration after dilution: 1.0 mass%) and stirred for 60 seconds. After that, Whatman filter paper no. The turbidity of the filtrate was measured with HACH 2100P type, and the cation demand of anion trash was measured with BTG PCD-03 type.
またマイクロピッチの測定は、白水を混合し水溶性高分子で処理した製紙原料を、ワットマン濾紙Ｎｏ．４１で濾過し、その濾液を厚さ０．２ｍｍのカウンティングチェンバー（ヘマサイトメーター）上に採取し、光学顕微鏡１２００倍で観察した。ピントを垂直方向にずらしていきながら静止画を複数枚撮影した。カウンティングチェンバー上の異なる５箇所以上で同様の操作を繰り返した。画像処理ソフト（Ｍｅｄｉａ Ｃｙｂｅｒｎｅｔｉｃｓ，ｉｎｃ． ＩＭＡＧＥ−ＰＲＯ ＰＬＵＳ Ｖｅｒ．５．０ を用い、顕微鏡画像の静止画を取込み、ＲＧＢ値のレンジ設定をＲ値（０−１９０）Ｇ値（０−１３０）Ｂ値（０−１５６）に調整することにより、目的とする粒子を抽出した。その抽出した粒子について、個数を測定した。 The micropitch is measured using a paperman raw material mixed with white water and treated with a water-soluble polymer. The filtrate was collected on a counting chamber (hemacytometer) having a thickness of 0.2 mm and observed with an optical microscope 1200 times. I took several still images while shifting the focus vertically. The same operation was repeated at five or more different locations on the counting chamber. Using image processing software (Media Cybernetics, inc. IMAGE-PRO PLUS Ver. 5.0), a still image of a microscopic image is captured, and the RGB value range setting is set to an R value (0-190) G value (0-130) B The target particles were extracted by adjusting the value (0-156), and the number of the extracted particles was measured.
さらにマイクロピッチが凝集し粗大化した成紙の欠陥となり得る粘着物の測定は、以下のように行った。すなわち白水を混合し水溶性高分子で処理した製紙原料を、直径９０ｍｍの円形濾紙（ワットマンＮｏ．４１、２０〜２５μｍ以上の粒子保持する）で５分間濾過し、濾過後の原料から濾紙を剥がし、剥がしたウェットシートを使用する。測定面は、剥がしたウェットシートの濾紙に面していない側の面とする。濾過量は、直径９０ｍｍの大きさで坪量１５０ｇ／ｍ２になるように、対象原料の濃度を計算して採取する。このウェットシートを濾紙に面していない側を測定面とし、ＳＵＳ板に張り合わせ、上の粘着物を媒体に転写する。この際、ウェットシートのＳＵＳ板（厚さ０．１ｍｍ）に張り付けた面と反対面に厚手の濾紙を合わせ、プレス機にセットし、４１０ＫＰａ、５分間加圧する。 Furthermore, the measurement of the sticky substance that could become a defect of the formed paper in which the micropitch was aggregated and coarsened was performed as follows. That is, a papermaking raw material mixed with white water and treated with a water-soluble polymer is filtered for 5 minutes with a circular filter paper having a diameter of 90 mm (holding particles of Whatman No. 41, 20 to 25 μm or more), and the filter paper is peeled off from the raw material after filtration. Use a wet sheet that has been peeled off. The measurement surface is the surface of the peeled wet sheet that does not face the filter paper. The filtration amount is collected by calculating the concentration of the target raw material so that the diameter is 90 mm and the basis weight is 150 g / m 2 . The side of the wet sheet that does not face the filter paper is used as a measurement surface, and the wet sheet is attached to a SUS plate, and the above adhesive is transferred to a medium. At this time, a thick filter paper is put on the surface opposite to the surface of the wet sheet attached to the SUS plate (thickness: 0.1 mm), set in a press machine, and pressurized at 410 KPa for 5 minutes.
次にウェットシートを張り付けたＳＵＳ板をロータリードライヤーにセットし、１０５℃で６分間加熱する。この際、ロータリードライヤーのシリンダー側にＳＵＳ板を、フェルト側は転写されたウェットシート側をセットする。 Next, the SUS plate with the wet sheet attached is set on a rotary dryer and heated at 105 ° C. for 6 minutes. At this time, the SUS plate is set on the cylinder side of the rotary dryer, and the transferred wet sheet side is set on the felt side.
加熱後、ＳＵＳ板上のウェットシートからの付着面（直径９０ｍｍ）中の任意の箇所２０箇所を選択し、実体顕微鏡を用いてデジタルカメラで撮影し、画像としてコンピュータに保存する。その後、マイクロピッチを測定した場合と同様の画像処理ソフトを用い、ＲＧＢ値のレンジ設定を調整することにより、目的とする粒子を抽出した。抽出した付着物の中から、大きさ、長短半径比、穴数、穴面積の最適条件下で再度抽出し、繊維分や他の付着物と、粘着性ピッチを判別する。その抽出した粒子について、粘着性ピッチ総面積、総個数を測定し、１ｍ２あたりに換算した。以上の結果を表６に示す。 After heating, 20 arbitrary locations on the adhesion surface (90 mm diameter) from the wet sheet on the SUS plate are selected, photographed with a digital camera using a stereomicroscope, and stored in a computer as an image. Then, the target particle | grains were extracted by adjusting the range setting of RGB value using the image processing software similar to the case where a micropitch was measured. The extracted deposits are extracted again under the optimum conditions of size, long / short radius ratio, number of holes, and hole area, and the sticky pitch is discriminated from the fiber content and other deposits. About the extracted particle | grains, the adhesive pitch total area and total number were measured, and it converted per 1 m < 2 >. The results are shown in Table 6.
（比較試験５）
実施例５と同様に表１の比較−５、比較−１０（ジメチルアミン／ポリアミン／エピクロロヒドリン重縮合物、重量平均分子量１２，０００）、比較−１１（ポリエチレンイミン（重量平均分子量５０，０００）、比較−１２（Ｎ−ビニルホルムアミド重合物の塩酸加水分解物、アミノ化率７０モル％、重量平均分子量１，２００，０００）に関して試験を実施した。結果を表６に示す。
(Comparative test 5)
As in Example 5, Comparative-5 in Table 1 and Comparative-10 (dimethylamine / polyamine / epichlorohydrin polycondensate, weight average molecular weight 12,000), Comparative-11 (polyethyleneimine (weight average molecular weight 50, 000) and Comparative-12 (hydrochloric acid hydrolyzate of N-vinylformamide polymer, amination rate 70 mol%, weight average molecular weight 1,200,000), the results are shown in Table 6.
（表６）
(Table 6)
Claims (5)
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキル基あるいはアルコキシル基であり、同種でも異種でも良い。Ａ１はＯまたはＮＨ、Ｂ１は炭素数２〜４のアルキレン基、Ｘ１ −は陰イオンをそれぞれ表す。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、Ｒ７は水素、炭素数１〜３のアルキル基であり、同種でも異種でも良い。Ａ２はＯまたはＮＨ、
Ｂ２は炭素数２〜４のアルキレン基、Ｘ２ −は陰イオンをそれぞれ表す。 2 to 40 mol% of a monomer represented by the following general formula (1), 2 to 50 mol% of a monomer represented by the following general formula (2), 1 to 30 mol% of itaconic acid, (meta ) Drainage improver or yield improvement comprising a water-soluble polymer having a weight average molecular weight of 16 to 30 million obtained by polymerizing monomers of 1 to 30 mol% of acrylic acid and 0 to 94 mol% of (meth) acrylamide Agent.
R 1 is hydrogen or a methyl group, and R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, which may be the same or different. A 1 is O or NH, B 1 is an alkylene group having 2 to 4 carbon atoms, X 1 - represents each an anion.
R 4 is hydrogen or a methyl group, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, R 7 is hydrogen and an alkyl group having 1 to 3 carbon atoms, and may be the same or different. A 2 is O or NH,
B 2 represents an alkylene group having 2 to 4 carbon atoms, and X 2 − represents an anion.
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキル基あるいはアルコキシル基であり、同種でも異種でも良い。Ａ１はＯまたはＮＨ、Ｂ１は炭素数２〜４のアルキレン基、Ｘ１ −は陰イオンをそれぞれ表す。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、Ｒ７は水素、炭素数１〜３のアルキル基であり、同種でも異種でも良い。Ａ２はＯまたはＮＨ、
Ｂ２は炭素数２〜４のアルキレン基、Ｘ２ −は陰イオンをそれぞれ表す。 2-10 mol% of a monomer represented by the following general formula (1), 2-10 mol% of a monomer represented by the following general formula (2), 1-20 mol% of itaconic acid, (meth) acrylic An interlayer strength improver or paper strength enhancer comprising a water-soluble polymer obtained by polymerizing monomers of 1 to 20 mol% of acid and 40 to 94 mol% of (meth) acrylamide.
R 1 is hydrogen or a methyl group, and R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, which may be the same or different. A 1 is O or NH, B 1 is an alkylene group having 2 to 4 carbon atoms, X 1 - represents each an anion.
R 4 is hydrogen or a methyl group, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, R 7 is hydrogen and an alkyl group having 1 to 3 carbon atoms, and may be the same or different. A 2 is O or NH,
B 2 represents an alkylene group having 2 to 4 carbon atoms, and X 2 − represents an anion.
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキル基あるいはアルコキシル基であり、同種でも異種でも良い。Ａ１はＯまたはＮＨ、Ｂ１は炭素数２〜４のアルキレン基、Ｘ１ −は陰イオンをそれぞれ表す。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、Ｒ７は水素、炭素数１〜３のアルキル基であり、同種でも異種でも良い。Ａ２はＯまたはＮＨ、
Ｂ２は炭素数２〜４のアルキレン基、Ｘ２ −は陰イオンをそれぞれ表す。 2-30 mol% of a monomer represented by the following general formula (1), 2-50 mol% of a monomer represented by the following general formula (2), 1-10 mol% of itaconic acid, (meth) acrylic A defect-generating inhibitor in papermaking comprising a water-soluble polymer obtained by polymerizing monomers of 1 to 10 mol% of acid and 0 to 94 mol% of (meth) acrylamide.
R 1 is hydrogen or a methyl group, and R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, which may be the same or different. A 1 is O or NH, B 1 is an alkylene group having 2 to 4 carbon atoms, X 1 - represents each an anion.
R 4 is hydrogen or a methyl group, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, R 7 is hydrogen and an alkyl group having 1 to 3 carbon atoms, and may be the same or different. A 2 is O or NH,
B 2 represents an alkylene group having 2 to 4 carbon atoms, and X 2 − represents an anion.
Ｒ８は水素またはＣＨ２ＣＯＯＹ２、ＱはＳＯ３、Ｃ６Ｈ４ＳＯ３、
ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３、Ｃ６Ｈ４ＣＯＯあるいはＣＯＯ、Ｒ９は水素、メチル基またはＣＯＯＹ３であり、Ｙ１、Ｙ２は水素または陽イオンをそれぞれ表わす。 A copolymer selected from the water-soluble polymer according to claim 1, one or more selected from monomers represented by the following general formula (3), and (meth) acrylamide, one selected from colloidal silica and bentonite A papermaking method comprising: combining the above and adding to the papermaking raw material before papermaking to make paper.
R 8 is hydrogen or CH 2 COOY 2 , Q is SO 3 , C 6 H 4 SO 3 ,
CONHC (CH 3 ) 2 CH 2 SO 3 , C 6 H 4 COO or COO, R 9 is hydrogen, a methyl group or COOY 3 , and Y 1 and Y 2 each represent hydrogen or a cation.
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