JP3998803B2 - Paper making method - Google Patents
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- JP3998803B2 JP3998803B2 JP08867598A JP8867598A JP3998803B2 JP 3998803 B2 JP3998803 B2 JP 3998803B2 JP 08867598 A JP08867598 A JP 08867598A JP 8867598 A JP8867598 A JP 8867598A JP 3998803 B2 JP3998803 B2 JP 3998803B2
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Description
【0001】
【発明の属する技術分野】
この発明は、抄紙における填料と微細繊維の歩留向上方法に関するものである。
【0002】
【従来の技術】
木材資源の保護からパルプ使用量の節約、及び印刷適性等の紙質の向上のため紙に填料を出来るだけ多量に内添させることが求められている。また、近年抄紙機の高速化が進み、紙のより効率的な生産が求められている。即ち、抄紙機のワイヤ−上での歩留まり、ろ水性の改善は重要な課題である。更に、機械パルプ及び/または脱墨パルプを多量に含む中質紙、下級紙に於いても、印刷適性などの点から填料を出来るだけ多量に内添させることが求められている。また、従来これ等中質紙、下級紙は酸性領域で抄造されて来たが、近年中性及び至アルカリ性領域で、しかも填料を多量に内添させることが求められている。
【0003】
従来の一般的な歩留向上方法は、硫酸バンドの添加に続いて比較的高分子量で低カチオン電荷密度のポリアクリルアミドを添加する(1)シングルポリマーシステムが使用されてきた。近年の抄紙機の高速化、用紙の軽量化、環境保全のための流失原料の最小化に対応するために、特開昭62-191598や特開平1-92498に示されている様に比較的高分子量で低カチオン電荷密度のポリアクリルアミド或いはカチオン澱粉の添加に続いて高アニオン電荷密度の膨潤性粘度鉱物であるベントナイト或いはコロイダルシリカを添加する(2)マイクロパーティクルシステムが用いられてきた。
【0004】
しかしながら、(1)のシングルポリマーシステムでは填料や微細繊維の歩留が十分でなく、(2)のアニオン性無機マイクロパーティクルを使用する場合には、比較的多量のアニオン性無機成分を必要とし、また、印刷時にアニオン性無機マイクロパーティクル由来の紙粉が発生することが問題視されていた。
【0005】
【発明が解決しようとする課題】
本発明の課題は、前述したような該当技術分野の要望にこたえ、かつ従来方法の次点を克服した填料や微細繊維の歩留まりを向上する方法を提供しようとするものである。
【0006】
【課題を解決するための手段】
本発明は、分子量が100万以上のカチオン性の水溶性高分子を添加後、アニオン性を呈し粒子径が200nm以下のアニオン性高分子マイクロパーティクルを紙料に添加することにより、抄紙における填料及び微細繊維の歩留まりを向上させる方法である。
【0007】
【発明の実施の形態】
以下に、本発明について詳しく説明する。
【0008】
本発明に使用するアニオン性高分子マイクロパーティクルは、下記の(a)〜(c)から重合され、粒子径が200nm以下のものである。
【0009】
(a)エチレン系不飽和単量体、
(b)アニオン性界面活性高分子、
(c)重合開始剤、
また、(a)が50〜95重量%、(b)が50〜5重量%、(c)が0.05〜0.5重量%で、アニオン性界面活性高分子を使用するマイクロエマルジョン重合法によって製造される。
【0010】
本発明の式1で規定する疎水性ビニルモノマーは、次式を有する。
【化3】
【0011】
その例としては、スチレン、α−メチルスチレン、ビニルトルエン、p-メチルスチレン、エチルスチレン、クロロスチレン、メチルアクリレート、エチルアクリレート、エチルメタクリレート、メチルメタクリレート、プロピルメタクリレート、ブチルメタクリレート、ペンチルメタクリレート等を挙げることができ、式1の一般的な化学構造を呈するラジカル重合可能なモノマーが使用できる。式1において、R1は、H又は炭素数1〜5を有するアルキル基であり、R2は、アリール基又はCOOR3(ここで、R3は炭素数1〜5を有するアルキル基を表す。)を表す。好ましい疎水性モノマーとしてはスチレン、α−メチルスチレン、ビニルトルエン、p-メチルスチレン、クロロスチレン、メチルアクリレート及びメチルメタクリレートの中から選ばれる。
【0012】
(b)アニオン性界面活性高分子は、(d)アニオン性モノマーと(a)疎水性ビニルモノマーの共重合体であり、(d)アニオン性モノマーは下式2で表される構造を示し、R4はカルボン酸基やそのカリウム、ナトリウム、アンモニウム塩、及びフェニルスルホン酸基である。R5はH、カルボン酸基やそのカリウム、ナトリウム、アンモニウム塩及びカルボン酸のメチルエステル、エチルエステル、ブチルエステルである。具体的には、マレイン酸、無水マレイン酸、フマル酸、マレイン酸のハーフエステル、アクリル酸、スチレンスルホン酸及びそのカリウム、ナトリウム、アンモニウム塩である。
【化4】
【0013】
重合開始剤はラジカル重合可能な全ての重合開始剤でよいが、過硫酸カリウム(KPS)などのアニオン性の重合開始剤が好ましい。
【0014】
分子量100万以上のカチオン性水溶性高分子としては、カチオン性ポリアクリルアミド、ポリジアリルジメチルアンモニウムクロリド、カチオン性デンプン等が好ましい。
【0015】
本発明の分子量 100 万以上のカチオン性水溶性高分子を、紙料へ添加後、アニオン性高分子マイクロパーティクルを添加することによって、填料や微細繊維の歩留まりを効果的に向上させることが可能である。この歩留まり機構は、従来のマイクロパーティクルと同様に架橋凝集であると考えられるが、アニオン性無機ナイクロパーティクルと異なり、ガラス転移点が約100℃のアニオン高分子マイクロパーティクルが抄紙機上での紙の乾燥時に繊維表面に拡散するので、紙粉を低減させることが可能である。
【0016】
アニオン高分子マイクロパーティクルの添加量としては、紙料の絶乾固形分に対して0.005重量%以上2.0重量%以下が好ましい。また、分子量100万以上のカチオン性水溶性高分子の添加量としては、紙料の絶乾固形分に対して0.005重量%以上2.0重量%以下が好ましい。
【0017】
【実施例】
以下に、本発明を実施例によって詳細に説明するが、本発明はこれらに限定されるものではない。
【0018】
[合成例1]機械的攪拌機を備え付けた反応器に、イオン交換水(90g)、スチレン(9.0g)、スチレン/マレイン酸共重合体(1.0g、商品名:コロパールM160、星光化学製)を仕込み、反応器の溶液を窒素ガスで30分間通じ、空気を置換して、60℃にまで加熱した。反応器の温度が60℃で安定した後に、重合開始剤として過硫酸カリウム(KPS)0.2gを5mlのイオン交換水に溶解したものを加えた。高分子合成は窒素を通じたまま500rpmで撹拌しながら6時間行った。得られたアニオン製高分子マイクロパーティクルは白色半透明状で、最終的な粒子径は120 nmであった。
【0019】
[合成例2]機械的攪拌機を備え付けた反応器に、イオン交換水(100g)、スチレン(9.0g)、スチレン/アクリル酸共重合体(1.0g、ハリマ化成製)を仕込み、反応器の溶液を窒素ガスで30分間通じ、空気を置換し、60℃まで加熱した。反応器の温度が60℃で安定した後に、重合開始剤としてKPS0.2gを5mlのイオン交換水に溶解したものを加えた。高分子合成は窒素を通じたまま500rpmで撹拌しながら6時間行った。得られたアニオン製高分子マイクロパーティクルは白色半透明状で、最終的な粒径は160 nmであった。
【0020】
[比較合成例1]
機械的攪拌機が備え付けてある反応器に100mlのイオン交換水、9.5gのスチレン、0.5gのスチレン/マレイン酸共重合体(星光化学製)を加えた。反応器の溶液を窒素ガスで30分間通じ、空気を置換し、60℃に安定させた。反応器の温度が60℃で安定した後に0.2gの重合開始剤KPSを5mlのイオン交換水に溶解したものを注入した。高分子合成は窒素を通じたまま500rpmで攪拌し、6時間行った。生成物は乳白色で、最終的な粒径は600nmであった。
【0021】
[実施例1]
200メッシュワイヤーのダイナミックドレネージジャー(DDJ)を使用して、微細繊維及び填料の歩留まりを測定した。DDJテスト時の攪拌速度は1000rpmで行った。50%の漂白広葉樹クラフトパルプと50%の漂白針葉樹クラフトパルプの混合パルプとパルプ固形分当たり20%の軽質炭酸カルシウム填料で構成されている0.5%濃度のパルプサスペンション500mlをDDJに加え、15秒攪拌後に対固形分0.5%の硫酸バンドを添加し、15秒間攪拌を続けた後に対紙料固形分当たり150ppmのカチオン性ポリアクリルアミド(商品名:DR-1500、ハイモ株式会社製))を添加し、15秒間攪拌後に合成例1で製造したアニオン性高分子マイクロパーティクル(APM)を対紙料固形分当たり0.025%〜0.2%添加し、15秒間攪拌を継続した後に、60秒間白水を採取した。白水を5Bのろ紙でろ過し、秤量し微細繊維及び填料の歩留まりを計算し、結果を表1に示した。
【0022】
[実施例2]
実施例1と同様の条件で、合成例2のAPMを使用して、 DDJテストを行って微細繊維及び填料の歩留まりを測定し、結果を表1に示した。
【0023】
[比較例1]
実施例1と同じ条件で、APMの添加率を0%にして、DDJテストを行って微細繊維及び填料の歩留まりを測定し、結果を表1に示した。
【0024】
[比較例2]
実施例1と同じ条件で、比較合成例1のAPMを添加してDDJテストを行って微細繊維及び填料の歩留まりを測定し、結果を表1に示した。
【0025】
[比較例3]
実施例1と同じ条件で、アニオン性高分子マイクロパーテクルの代りにスチレン/アクリル酸共重合体(ハリマ化成製)を添加してDDJテストを行って微細繊維及び填料の歩留まりを測定し、結果を表1に示した。
【0026】
【表1】
【0027】
下記の表2より、紙料に、高分子量のカチオン性ポリアクリルアミドを添加後、粒子径200nm以下のアニオン性高分子マイクロパーティクルを添加することによって、微細繊維及び填料の歩留まりは向上する。
【0028】
【表2】
【0029】
【発明の効果】
本発明によって、抄紙系における填料と微細繊維の歩留まりを大幅に向上させることが可能となる。また、抄紙機のインレット濃度を低下できるので、紙の坪量変動を抑え、地合いを向上させ、流失原料の削減を図ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for improving the yield of fillers and fine fibers in papermaking.
[0002]
[Prior art]
In order to save wood resources and save paper, and to improve paper quality such as printability, it is required to add as much filler as possible to paper. In recent years, the speed of paper machines has been increased, and more efficient production of paper has been demanded. That is, improvement in yield and freeness on the wire of a paper machine is an important issue. Further, even in medium-quality paper and lower grade paper containing a large amount of mechanical pulp and / or deinked pulp, it is required to add as much filler as possible from the viewpoint of printability. Conventionally, these medium quality paper and lower grade paper have been made in the acidic region, but in recent years, it has been required to add a large amount of filler in the neutral and extremely alkaline region.
[0003]
Conventional general yield enhancement methods have used (1) single polymer systems in which polyacrylamide with a relatively high molecular weight and low cationic charge density is added following the addition of the sulfate band. In order to cope with the recent increase in the speed of paper machines, the reduction in paper weight, and the minimization of lost materials for environmental protection, as disclosed in JP-A-62-191598 and JP-A-1-92498, 2. Addition of high molecular weight, low cation charge density polyacrylamide or cationic starch followed by high anion charge density swellable viscosity mineral bentonite or colloidal silica (2) Microparticle systems have been used.
[0004]
However, in the single polymer system of (1), the yield of fillers and fine fibers is not sufficient, and when using the anionic inorganic microparticles of (2), a relatively large amount of anionic inorganic component is required, Further, it has been regarded as a problem that paper powder derived from anionic inorganic microparticles is generated during printing.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to meet the above-mentioned demands in the technical field and to provide a method for improving the yield of fillers and fine fibers that has overcome the next point of the conventional method.
[0006]
[Means for Solving the Problems]
In the present invention, after adding a cationic water-soluble polymer having a molecular weight of 1 million or more, anionic polymer microparticles having an anionic property and a particle diameter of 200 nm or less are added to the paper material. This is a method for improving the yield of fine fibers.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0008]
The anionic polymer microparticles used in the present invention are polymerized from the following (a) to (c) and have a particle diameter of 200 nm or less.
[0009]
(A) an ethylenically unsaturated monomer,
(B) an anionic surfactant polymer,
(C) a polymerization initiator,
In addition, a microemulsion polymerization method using an anionic surfactant polymer, wherein (a) is 50 to 95% by weight, (b) is 50 to 5% by weight, and (c) is 0.05 to 0.5% by weight. Manufactured by.
[0010]
The hydrophobic vinyl monomer defined by Formula 1 of the present invention has the following formula:
[Chemical 3]
[0011]
Examples include styrene, α-methyl styrene, vinyl toluene, p-methyl styrene, ethyl styrene, chlorostyrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, methyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, and the like. And free-radically polymerizable monomers exhibiting the general chemical structure of Formula 1 can be used. In Formula 1, R 1 is H or an alkyl group having 1 to 5 carbon atoms, R 2 is an aryl group or COOR 3 (wherein R 3 represents an alkyl group having 1 to 5 carbon atoms). ). Preferred hydrophobic monomers are selected from styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, chlorostyrene, methyl acrylate and methyl methacrylate.
[0012]
(b) the anionic surface-active polymer is a copolymer of (d) an anionic monomer and (a) a hydrophobic vinyl monomer, and (d) the anionic monomer has a structure represented by the following formula 2. R 4 is a carboxylic acid group or its potassium, sodium, ammonium salt, or phenylsulfonic acid group. R 5 is H, carboxylic acid group or its potassium, sodium, ammonium salt and carboxylic acid methyl ester, ethyl ester, butyl ester. Specifically, maleic acid, maleic anhydride, fumaric acid, maleic acid half ester, acrylic acid, styrene sulfonic acid and its potassium, sodium and ammonium salts.
[Formula 4]
[0013]
The polymerization initiator may be any polymerization initiator capable of radical polymerization, but an anionic polymerization initiator such as potassium persulfate (KPS) is preferred.
[0014]
As the cationic water-soluble polymer having a molecular weight of 1 million or more, cationic polyacrylamide, polydiallyldimethylammonium chloride, cationic starch and the like are preferable.
[0015]
It is possible to effectively improve the yield of fillers and fine fibers by adding anionic polymer microparticles after adding the cationic water-soluble polymer having a molecular weight of 1 million or more of the present invention to the stock. is there. This yield mechanism is considered to be cross-linked aggregation like conventional microparticles, but unlike anionic inorganic nicroparticles, anionic polymer microparticles with a glass transition point of about 100 ° C are used on paper machines. It is possible to reduce paper dust because it diffuses on the surface of the fiber during drying.
[0016]
The addition amount of the anionic polymer microparticles is preferably 0.005% by weight or more and 2.0% by weight or less based on the absolutely dry solid content of the paper. The addition amount of the cationic water-soluble polymer having a molecular weight of 1 million or more is preferably 0.005% by weight or more and 2.0% by weight or less based on the absolutely dry solid content of the paper.
[0017]
【Example】
EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
[0018]
[Synthesis Example 1] In a reactor equipped with a mechanical stirrer, ion-exchanged water (90 g), styrene (9.0 g), styrene / maleic acid copolymer (1.0 g, trade name: Colopearl M160, manufactured by Hokko Chemical Co., Ltd.) The reactor solution was charged with nitrogen gas for 30 minutes to replace the air and heated to 60 ° C. After the reactor temperature was stabilized at 60 ° C., 0.2 g of potassium persulfate (KPS) dissolved in 5 ml of ion exchange water was added as a polymerization initiator. Polymer synthesis was performed for 6 hours while stirring at 500 rpm while passing nitrogen. The obtained anionic polymer microparticles were white translucent and the final particle size was 120 nm .
[0019]
[Synthesis Example 2] A reactor equipped with a mechanical stirrer was charged with ion-exchanged water (100 g), styrene (9.0 g), and a styrene / acrylic acid copolymer (1.0 g, manufactured by Harima Chemical Co., Ltd.). Was passed through with nitrogen gas for 30 minutes to replace the air and heated to 60 ° C. After the reactor temperature was stabilized at 60 ° C., 0.2 g of KPS dissolved in 5 ml of ion exchange water was added as a polymerization initiator. Polymer synthesis was performed for 6 hours while stirring at 500 rpm while passing nitrogen. The obtained anionic polymer microparticles were white translucent and the final particle size was 160 nm .
[0020]
[Comparative Synthesis Example 1]
To a reactor equipped with a mechanical stirrer, 100 ml of ion exchange water, 9.5 g of styrene, 0.5 g of styrene / maleic acid copolymer (manufactured by Seiko Chemical) were added. The reactor solution was flushed with nitrogen gas for 30 minutes to displace air and stabilize at 60 ° C. After the reactor temperature was stabilized at 60 ° C., 0.2 g of a polymerization initiator KPS dissolved in 5 ml of ion exchange water was injected. Polymer synthesis was carried out for 6 hours while stirring at 500 rpm while passing nitrogen. The product was milky white and the final particle size was 600 nm.
[0021]
[Example 1]
A 200 mesh wire dynamic drainage jar (DDJ) was used to measure the yield of fine fibers and filler. The stirring speed during the DDJ test was 1000 rpm. Add 500 ml of 0.5% pulp suspension consisting of 50% bleached hardwood kraft pulp and 50% bleached softwood kraft pulp and 20% light calcium carbonate filler per pulp solids to DDJ and stir for 15 seconds Later, a sulfuric acid band with a solid content of 0.5% was added, and after stirring for 15 seconds, 150 ppm of cationic polyacrylamide (trade name: DR-1500, manufactured by Hymo Co., Ltd.) per solid content of the paper was added, After stirring for 15 seconds, 0.025% to 0.2% of the anionic polymer microparticle (APM) produced in Synthesis Example 1 was added per solid content of the paper, and stirring was continued for 15 seconds, and then white water was collected for 60 seconds. White water was filtered through 5B filter paper, weighed, and the yields of fine fibers and filler were calculated. The results are shown in Table 1.
[0022]
[Example 2]
Using the APM of Synthesis Example 2 under the same conditions as in Example 1, DDJ tests were performed to measure the yields of fine fibers and fillers, and the results are shown in Table 1.
[0023]
[Comparative Example 1]
Under the same conditions as in Example 1, the APM addition rate was 0%, DDJ test was performed to measure the yield of fine fibers and filler, and the results are shown in Table 1.
[0024]
[Comparative Example 2]
Under the same conditions as in Example 1, the APM of Comparative Synthesis Example 1 was added and a DDJ test was performed to measure the yields of fine fibers and filler. Table 1 shows the results.
[0025]
[Comparative Example 3]
Under the same conditions as in Example 1, a styrene / acrylic acid copolymer (manufactured by Harima Chemicals) was added instead of an anionic polymer microperticle and DDJ test was performed to measure the yield of fine fibers and fillers. Is shown in Table 1.
[0026]
[Table 1]
[0027]
From Table 2 below, the yield of fine fibers and filler is improved by adding high molecular weight cationic polyacrylamide to the paper and then adding anionic polymer microparticles having a particle diameter of 200 nm or less.
[0028]
[Table 2]
[0029]
【The invention's effect】
According to the present invention, the yield of fillers and fine fibers in a papermaking system can be greatly improved. Moreover, since the inlet concentration of the paper machine can be reduced, the basis weight fluctuation of the paper can be suppressed, the texture can be improved, and the loss of lost material can be reduced.
Claims (2)
前記アニオン性高分子マイクロパーティクルは、
(a)式1:
で表されるエチレン系不飽和単量体、
(b)式2:
で表されるアニオン性モノマーと前記(a)のエチレン系不飽和単量体との共重合体から成るアニオン性界面活性高分子、及び
(c)重合開始剤、
からマイクロエマルジョン重合法によって合成されたものであることを特徴とする、前記抄紙方法。In the papermaking method, a cationic water-soluble polymer having a molecular weight of 1 million or more is added to the paper, and then anionic polymer microparticles having a particle size of 200 nm or less are added.
The anionic polymer microparticles are:
(A) Formula 1:
An ethylenically unsaturated monomer represented by
(B) Formula 2:
An anionic surfactant composed of a copolymer of an anionic monomer represented by formula (a) and an ethylenically unsaturated monomer of (a), and
(C) a polymerization initiator,
The papermaking method, wherein the papermaking method is synthesized by a microemulsion polymerization method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP08867598A JP3998803B2 (en) | 1998-04-01 | 1998-04-01 | Paper making method |
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JP08867598A JP3998803B2 (en) | 1998-04-01 | 1998-04-01 | Paper making method |
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Publication Number | Publication Date |
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JPH11286890A JPH11286890A (en) | 1999-10-19 |
JP3998803B2 true JP3998803B2 (en) | 2007-10-31 |
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JP08867598A Expired - Fee Related JP3998803B2 (en) | 1998-04-01 | 1998-04-01 | Paper making method |
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